ORGANIC CHEMISTRY NOTES

CHAPTER 1

INTRODUCTION

What is Organic chemistry?

Is the branch of chemistry that deals with the study of compounds of carbon

All organic compounds contain carbon together with one or more other elements such as
hydrogen, oxygen, chlorine, Nitrogen and sulphur

These organic compounds range from simple molecules such as methane, ethene, ethyne, giant
molecules such as Deoxyribonucleic acid (DNA),rubber, cotton, drugs, insecticides, explosives
and photographic films- of which all these compounds are of great importance in everyday life

Organic chemistry is also the foundation for basic studies in Botany, nutrition, agriculture,
pharmacy, technology, forestry, zoology etc

UNIQUENESS OF CARBON IN ORGANIC COMPOUNDS

Carbon behaves differently from the rest of the group members due:

 Small Atomic radius

 High electronegativity

 Lack of vacant orbital

Some of the properties in which Carbon differs from the rest of the members include:

 It forms a stable multiple bonds with itself and with other non-metals.

 Carbon can form a number of hydrocarbons because it can catenate. Catenation

is the ability of the element to form bonds between atoms of the same element.

 It forms gaseous oxides unlike other members

 The halides are stable to hydrolysis.

CHARACTERISTIC PROPERTIES OF ORGANIC COMPOUNDS

Most organic compounds are:

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  Covalently bonded and generally gases, volatile liquids and low melting point
solids with few elements such as carbon, hydrogen, sulphur, nitrogen and
halogens

 Low melting and boiling point compounds

 Generally insoluble in water except those with polar functional groups such as
OH, COOH, SO3H

 The reactions are generally slow although some are explosive and most reactions
require catalysts

REACTANTS AND REACTIONS

In chemical reactions, the reactants molecules are that are attacked are called SUBSTRATE but
the general term given to the attacking substrate is called a REAGENT.

Substrates and Reagents usually interact to yield the products involve redistribution of
electrons.

Generally there are two ways in which a covalent bond can be broken include:

(a) Homolytic cleavage

In this type, the bond is broken symmetrically and each atom remains with one electron
to form a radical. Example include

B A A + B

These types of reactions are usually catalysed by:

 Ultraviolet light or short wavelength light or sunlight

 High temperatures

 Peroxide

(b) Heterolytic cleavage

In this of the reactions, the bonds are broken unsymmetrically generating cation and anion

If the molecule contains different atoms with different electronegativity, the tendency of ions
formation differs.

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These breakages usually take place in solvents of high ionizing power which is catalysed by ionic
polar catalysts

Example include: If A is more electronegative than B, then

B A A- + B+

CARBOCATION OR CARBONIUM IONS

These are formed when fragments of a molecule in which a group and the bonding electrons
are removed from the carbon chain

Carbocations are divided into 10, 20 and 30

The stability of the Carbocations depend on the number of the electron releasing group e.g. CH 3
and is expressed as 30> 20> 10

ELECTROPHILES AND NUCLEOPHILES

Electrophiles are species which are electron loving since they are electron deficient while
Nucleophiles are species which are electron rich

Examples of Electrophiles and Nucleophiles include:

+
NO2 , H+, Cl+, Br+,R3C+ and RN2+
Electrophiles:

- - - -
Nucleophiles: H2O, ROH,RO , OH, Br CN and NH3

HYDROCARBONS

These compounds that contain carbon and hydrogen as the only elements present.

They are classified as:

(a) Saturated hydrocarbons

These are hydrocarbons that contain a carbon- carbon single bond e.g. in Alkanes

(b) Unsaturated hydrocarbons

These are hydrocarbons that contain multiple bonds between the carbon atoms e.g Alkenes

Further classification includes:

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 (a) Aliphatic Hydrocarbons

These are hydrocarbons that contain low carbon-hydrogen ratio. Usually on burning, they burn
with a non-sooty flame.

(b) Aromatic hydrocarbons

These are hydrocarbons that contain a high carbon- hydrogen ratio. Usually on burning, they
burn with a sooty flame. These compounds are usually considered as derivatives of benzene.

N.B Also Alicyclic hydrocarbons which are hydrocarbons in which carbon atoms are arranged
in the ring other than benzene ring e.g

FUNCTIONAL GROUPS AND HOMOLOGOUS SERIES

Homologous series is a series in which organic compounds can be placed. The characteristics of
homologous series include;

 Member of a homologous series can be represented by a general formula e.g. CnH2n+2 for
Alkanes, CnH2n for Alkenes

 Each member of a series has a similar method of preparation

 Members in a given series has a similar chemical properties to each other

 As a series is ascended down, a methylene group is added to each successive member

therefore physical properties such as boiling and melting points change slightly.

 Several homologous series are regarded as alkane derivatives since the hydrogen atom in
the alkane is replaced by a functional group

Functional group is atom or group of atoms which impart specific chemical properties to the
chemical compounds containing then regardless of the nature of the hydrocarbon part of the
molecule.

Generally Organic compounds are classified based upon the functional group because
compounds having the same functional groups have the similar chemical properties.

The table below shows some of the examples of functional groups:

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Name Structural formula Examples
Alkane RH or CnH2n+2 CH3CH2CH3
Alkenes RCH=CH2 or CnH2n CH3CH=CH2
Alkynes RC CR
or C H
n 2n-2
CH3C CCH3

Halogen compounds RCH2X (x=Cl, Br and I) CH3CH2Cl

Alcohols RCH2OH or CnH2n+1OH CH3CH2OH
Carbonyl compounds Aldehydes: RCHO or CH3CH2CHO
CnH2n+1CHO
Ketones: RCOR or CH3COCH3
CnH2n+2CO
Carboxylic acids RCH2COOH or CH3COOH
CnH2n+1COOH
Amines RCH2NH2or CnH2n+1COOH CH3CH2NH2,CH3NHCH3
Ethers ROR or CnH2n+1O CH3CH2OCH3

TYPES OF ORGANIC REACTIONS

Organic reactions are usually initiated by Electrophiles or Nucleophiles or free radical attack
upon the substrate. These reactions include:

(a) Substitution or Displacement reactions

These reactions involve the direct displacement of an atom or group by another atom or group.

The number of atoms displaced depends on the nature of the reactants and conditions under
which the reaction is carried out.

Generally they are represented as;

H H
H H

Y + Z H C C Z +Y
H C C

H H
H H

e.g.

NaOH (aq)
CH3CH2Cl CH3CH2OH + NaCl
Heat

Substitution reactions are divided into two classes:

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 (i) Nucleophilic substitution reaction (SN).

These are reactions whereby electron rich species simply displaces an atom or group. These
reactions are undergone by Alkyl halides.

(ii) Electrophilic substitution reaction (SE)

These are reactions where by electron deficient group displaces an atom. These reactions are
undergone by Benzene where hydrogen atom is replaced by an electron deficient group

According to the number of species involved in the formation of the activated complex in the
rate determining step, Nucleophilic substitution reaction is divided into two:

(i) Nucleophilic substitution unimolecular (SN1) where a single species is involved.

(ii) Nucleophilic substitution Bimolecular (SN2) where two species are involved.

(b) Elimination reactions

These are reactions involve the removal of atoms or groups of atoms from two adjacent atoms
to form a multiple bond or unsaturated compound.

These reactions are usually encountered to yield alkenes and alkynes

Generally they are represented as;

H H
H

H C C H H C C H + YZ

Y Z H

e.g.

Conc.H2SO4
CH3CH2OH H2C CH2 + H2O
o
180 C

Elimination reaction is also divided into two types based upon the number of species involved
in the formation of activated complex in the rate determining step.

(i) Elimination Unimolecular (E1) e.g dehydrohalogenation and dehydration of 30 Alkyl halides
and Alcohols respectively

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(ii) Elimination Bimolecular (E2) e.g dehydrohalogenation and dehydration of 20 Alkyl halides
and Alcohols.

(c) Addition reactions

These are reactions wherebythe attacking reagent simply adds across the unsaturated bond of
the reactant to saturated product.

These reactions are usually the reverse of the elimination reactions and the unsaturated
reactants act as Nucleophiles and consequently more vulnerable to attack by Electrophiles.

These are reactions are generally represented as:

Y Z

YZ H C H
H2C CH2 C

H H

Example include

HBr

Br

Addition reactions are divided into classes:

(i) Electrophilic addition reactions (AE)

These are reactions where the electron loving species simply adds itself to unsaturated
compound e.g. addition reactions of alkenes and alkynes.

(ii) Nucleophilic addition reactions (AN)

These are reactions where the electron rich species simply adds itself to the unsaturated bond
of the bond e.g. addition reactions of carbonyl compounds

(d) Rearrangement reactions

These are reactions which involve the migration of an atom or group from one site to another
within the same molecule. It involve the migration of a functional group from one position to
another within the same molecule

Example include

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 RCHCH C H2 RCH CHCH2 Br

Br

MECHANISM OF ORGANIC REACTIONS

Mechanisms of reaction are sequence steps by which the reactions take place from start to the
end. The mechanism is worked out from a study of the kinetics of the reactions. Other method
include spectroscopy and use of radioactive isotopes

ISOMERISM

This is the existence of different compounds with the same molecular formulae but different
structural formulae.

Compounds with same molecular formulae but different structural formulae are known as
Isomers. Isomerism is divided into two classes:

(a) Structural Isomerism

This is the type of isomerism which shows the sequence in which the atoms in a molecule are
bonded or linked.

It is divided into three classes:

(i) Chain Isomerism. This is the type of structural isomerism where by the isomers differ in
the carbon chain. The isomers usually have the same functional group and belong to the same
homologous series.

It can be divided into classes’ i.e. Straight chain and branch chain

Example included: Q has molecular formula C4H10, write down possible chain structural
formula of Q. Since the M.F. is C4H10 isomers are:

CH3CH2CH2CH3 and CH3CHCH3

CH3

(ii) Positional Isomerism. This is the isomerism where the substituent groups are in
different positions in the same carbon skeleton. The isomers are chemically similar because
they possess the same functional groups

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 CH3CH2CH CH2 and CH3CH CHCH3
CH3CH2CH2OH and CH3CHCH3

OH

(iii) Functional Isomerism. This is the isomerism where by the isomers in different
homologous series have different functional groups.

Examples include:

(a) A compound Q has Molecular formula C2H6O

 The isomers are CH3CH2OH (from Alcohol) and CH3OCH3 (from ether)
(b) A compound W has molecular formulaC3H6O

 The isomers are CH3COCH3 (from Ketones) and CH3CH2CHO (from Aldehydes)
(c) A compound Z has molecular formula C4H8O2

 The isomers are CH3CH2CH2COOH (from Carboxylic acid) and

CH3COOCH2CH3 (from Esthers)

(b) Stereoisomerism

This is the type of isomerism where by the compounds have the same molecular formula
and same structural formula but differ in the spatial arrangement of the bonds.

Stereoisomerism is divided into two classes:

(i) Cis-trans Isomerism (Geometrical Isomerism)

This occurs in compounds in which free rotation is prevented by the presence of multiple
bonds, a ring or steric factors.

Geometrical Isomers differ in spatial arrangement giving rise to Cis isomers which has
identical atoms or groups on the same side of the multiple bond and a Trans isomers
which has the atoms or groups in opposite side.

Examples include:

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 H HOOC
COOH H

C
C
and
C
C
H COOH
H COOH
Trans-isomers
Cis-isomers

(ii) Optical Isomerism

This occurs in compounds with four atoms or groups attached to the same carbon such that the
isomers obtained are not super imposable on the mirror images.

These isomers which are not super imposable are referred as to as Enantiomers and the
structures are said to be chiral.

Example includes:

Mirror

H
H

C
C
HO CH2CH3
CH3CH2 OH
CH3 CH3

Object Image

Enantiomers have same physical properties but may be distinguished from each other by the
ability they rotate polarized light due to optical activity.

If the rotation of the plane is in clockwise direction (to the right), the substance is
dextrorotatory (with + sign) while if the rotation is in the anticlockwise (to the left), the
substance is laevorotatory (with – sign)

The degree of rotation is determined by use of a polarimeter.

METHODS OF RELATIVE MOLECULAR MASS DETERMINATION OF ORGANIC COMPOUNDS

The four commonly used methods for determining the relative molar mass of organic
compounds include:

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(a) Vapour density measurements using gas syringe or Victor Meyer’ s method

Example

A hydrocarbon Q contains 91.3% carbon and the rest hydrogen.

(a) Determine the empirical formula of Q (C=12, H=1)

(b) The vapour density of Q is 39 at a constant temperature and pressure.

Determine the:

(i) Molecular mass of Q

(ii) Molecular formula of Q

(c) Q burns with a sooty flame, write down the possible isomer(s) of Q

Soln:

(a) Elements: C H

Masses (%): 91.3 8.7

91.3 8 .7
Moles:
12 1

= 7.6083 8.7

7.6083 8.7
Mole ratio: :
7.6083 7.6083

= 1 : 1

 E.F. of Q is CH
M .mass
(b) (i) From  v.density M .mass  39  2  78 g
2

(ii) From M.F= (E.F) n = M .mass

(CH ) n  78 Or n (12+1) = 78 n  6

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  M .F Of Q is C6H6

(c) The molecular structure of Q is

Example

When 0.29g of substance Q was burnt in oxygen, 0.66g of carbondioxide and 0.27g of water
were formed.

(a) Calculate the empirical formula of Q

(b) Q forms a yellow solid with 2, 4-dintrophenylhydrazine. The vapour density of Q is 29.

(i) Write the structural formulae of the isomers and names of Q

(ii) What type of structural isomerism is exhibited by Q.?

(iii) How can the structural isomers be differentiated

Soln:

(a) RFM of CO2 = 1(12) + 2(16) = 44 Elements: C H O

RFM of H2O = 2(1) + 1 (16) = 18 Masses (g): 0.18 0.03 0.08

1(12) 0.18 0.03 0.08

Mass of Carbon in Q =  0.66  0.18 g moles:
44 12 1 16
= 0.015 0.03 0.005

2(1) 0.015 0.03 0.005

Mass of Hydrogen in Q =  0.27  0.03g Ratio:
18 0.005 0.005 0.005

 Mass of Oxygen in Q = 0.29- (0.18+ 0.03) 3: 6 : 1

= 0.08g  E.F. of Q is C3 H6 O

(b) (i) M. mass of Q = 29×2 = 58g  (C3H6O)n = 58

 n(3(12) +6(1) + 1 (16)) = 58 or 58n = 58 or n= 1

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 M.F of Q is C3H6O with S.F CH3COCH3 –Propanone and CH3CH2CHO- Propanal

(ii) Functional Isomerism

(iii) By using Ammoniacal Silver nitrate solution

Example

(a) Define the hydrocarbon

(b) A compound X, on combustion gave 0.629g of carbondioxide and 0.257g of water.

Determine the empirical formula of X

(c) When 0.10g of X was vapourised, it occupied a volume of 40cm3 at s.t.p

(i) Calculate the molecular mass of X

(ii) Determine the molecular mass of X hence write the structural formulae of the possible
isomers

Soln:

(a) A compound that contains carbon and hydrogen as the only elements present

1(12)
(b) Mass of Carbon =  0.629  0.1715 g (ii) (CH2) n = 56
44

2(1)
Mass of Hydrogen =  0.257  0.0286 g n (12+2) = 56  n  4
18

Elements: C H  M.F of X is C4H8

0.1715 0.0286
Moles:
12 1

CH3C CH2
CH3
= 0.0143 0.0286

Hence mole ratio = 1:2  E.F of X is CH2 CH3CH2CH CH2

mRT CH3CH CHCH3

(c) (i) From PV = nRT  Mr 
PV

0.1  8.314  273

=  56 g
101325  40  10 6

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(b) Colligative Properties of dilute solutions containing non-volatile solutes

These include lowering of vapour pressure, cryoscopy, ebullioscopy and osmotic pressure

Cryoscopic method has an advantage over Ebullioscopic method that it is not affected very
much by pressure changes of which boiling points depend on the atmospheric pressure

Molecular mass of polymers is determined using Osmotic pressure because they are easily
denatured by heat and a amount of polymer changes the osmotic pressure of the solvent
significantly.

Example

A compound W contains Carbon, Hydrogen and oxygen. When 1.5g of W was burnt in excess
oxygen, 1.467g of carbon dioxide and 0.297g of water were formed.

(a) Determine the empirical formula of W

(b) 7.5g of W was dissolved in 204.4g of water to a solution .The prepared boiled at
100.212oC.

The boiling point constant of water is 0.52oC per mole per kg.

Determine the:

(i) Molecular mass of W

(ii) Molecular formula

(iii) Structural formula of w

(c) State the condition(s) employed in order for W to react with following compounds.

In each case write the equation of reaction

(i) Sulphuric acid

(ii) Potassium manganate (VII) solution

(d) Name the reagent that can be used to distinguish between W and Methanoic acid.

Soln:

2 12
(a) Mass of hydrogen =  0.297 = 0.033g, Mass of Carbon =  1.467  0.40 g
18 44

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  Mass of oxygen = 1.5- (0.033+0.40) = 1.067g

Elements: C H O 0.033 0.033 0.067

0.40 0.033 1.067

Moles:  Mole ratio: 1: 1: 2
12 1 16

 E.F of W is CHO2

T  100.212  100  0.212 o C

(b) (i) 204.4g of water contains 7.5g of W

7.5
 1000g of water contains  1000  36.69 g of W.
204.4

0.212oC is the elevation in b.p.t caused by 36.69g of W

36.69
o
 0.52 C is the elevation in b.p.t caused by  0.52  90 g of W
0.212

90
(ii) (CHO2)n= 90 n =  2  M.F of W is C2H2O4
45
COOH

(iii) COOH

(c) (i) Concentrated acid and heat

Conc.H2SO4
H2C2O4 H2O + CO + CO2
Heat

(ii) Acidified Potassium permanganate solution and warm the solution to about 70 oC
5C2O42- (aq) + 2MnO4- (aq) + 16H+ (aq) 10CO2 (g) + 2Mn2+ (aq) + 8 H2O (l)

(d) Ammoniacal Silver nitrate solution

Example

(a) Differentiate between Diffusion and Osmosis

(b) The osmotic pressure of a solution containing 4.00gdm-3 of polyvinylchloride,

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 CH2=C H

Cl n

In dioxin is 65Pa at 20oC. Determine the number of monomers, n, in the polymer.

(c) State two conditions under which the Osmotic laws cannot be obeyed

Soln

(a) Diffusion is the movement of molecules from high concentrated area to a low
concentrated area while Osmosis is the movement of solvent molecules from a dilute
solution to concentrated solution across a semi-permeable membrane

mRT 4  8.314  293

(b) From v  nRT  Mr  =  149.91  10 3
V 65  10 3

 n (24+3 + 35.5)=149.91X10  n  2399

3

(c) When the solution is concentrated

When the solute associate or dissociate in the solvent

(c) Eudiometry method or Gaseous explosion

This method is suitable for gaseous hydrocarbon only

Example

(a) State Gay-Lussac’ s law.

(b) 30cm3 of a gaseous hydrocarbon Y burnt at constant temperature and pressure produced
120cm3 of carbon dioxide and 120cm3 of steam.

(i) Determine the formula of Y.

(ii) Write structures and names of all the isomers of Y.

Soln

(a) When gases combine together at a constant temperature and pressure they do so in
volumes which bear a simple ratio to each other and to the volume of gaseous product.

(b) (i)

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 CxHy + (x+y/4) O2 xCO2 + y/2H2O

30cm3 30(x+y/4)cm3 30xcm3 15ycm3

15y=120 or y= 8
30x=120 or x=4 C4H8

(ii)

CH3CH2CH CH2 CH3CH CHCH3 CH3C CH2

CH3

Example

30cm3 of gaseous hydrocarbon were mixed with 140cm3 of excess oxygen and exploded. After
cooling to room temperature the residual gases occupied 95cm3. By absorption with potassium
hydroxide solution a diminution of 60cm3 was produced. Determine the molecular mass of the
hydrocarbon

Soln

CxHy + (x+ y/4) O2 xCO2 + y/2 H2O

3ocm3 30(x+y/4) cm3 30xcm3 15ycm3

 Volume of excess oxygen = 95-60 = 35cm3

Volume of Oxygen used = 140-35= 105cm3

Also Volume of carbondioxide produced= 60cm3

60 y 105
 30x=60 or x=  2 Also ( x  )   3.5 or y=6
30 4 30

M.F of the hydrocarbon is C2H6 with molecular mass = 2(12) + 6(1) = 30g

(d) Steam Distillation

This is the technique of separating a volatile substance that is immiscible with water from
a non-volatile component at a temperature below its boiling point.

This method helps in separating organic compounds that decompose near their boiling
point and distil at a temperature below their boiling points.

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 It uses the principle of

n1 p
 1 Where n1 and n2 are moles of component 1 and 2 respectively with vapour
n2 p2
pressure P1 and P2 respectively

m1 W1 p1
  Where W1 and W2 are the molecular mass of 1 and 2 respectively
m 2 W2 p 2

Example

(a) When 4.9g of an organic compound X was burnt in excess oxygen, 14.78g of carbondioxide
and 5.38g of steam was formed. Calculate the simplest formula of X

(b) X was steam distilled at 80oC and 760mmHg and the distillate was found to contain
90.8% by mass of X. The vapour pressure of water at the same temperature is
240mmHg.

(i) Calculate the formula mass of X

(ii) Deduce the molecular formula of X

(iii) Write down the possible isomers of X

12
Soln:Mass of Carbon =  14.78  4.304 g
44

2
Mass of Hydrogen=  5.38  0.598 g
18

Elements: C H

4.304 0.598
Moles:
12 1

Ratio 1 : 1.667

 3 : 5 hence E.F. of X is C3H5

m1 W1 p1
(b) (i) From   PT =P1+ P2 or P2= 760-240 = 520mmHg and
m 2 W2 p 2
m1 = 100 - 90.8 = 9.2

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 9.2 18  240
 W2  81.99 g
90.8 W2  520

82
(ii) (C3H5) n = 82 or n =  2  M.F of X is C6H10
41

(iii) The isomers are

CH3CH2CH2CH2C CH CH3CH2CH2C CCH3 CH3CH2C CCH2CH3

CH3
CH3CHC CCH3 CH2 CHCH2CH2CH CH2
CH3CC CH

CH3
CH3

CH3

N.B. Check Physical Chemistry Textbook for more questions in order to practice

CHAPTER TWO

ALKANES

These are hydrocarbons which form a homologous series of saturated nature with a general
formula CnH2n+2. Successive members differ in composition by a methylene group

The main sources of Alkanes include:

 Natural gas which mainly contains methane with low amounts or propane and butane

 Petroleum products which are separated by fractional distillation during a process of

refining

Cracking

This is the breaking down of long chain organic molecules (hydrocarbon) into two or small
molecules which are useful products.

Cracking can be done using a catalyst (catalytic cracking) or by using high temperature (thermal
cracking), the alkenes are used to make other chemical and alkanes are used for fuels.

NOMENCLATURE/NAMING OF ALKANES

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With exception of the first four members of the homologous series, the straight chain members
are named by taking prefix appropriate to the number of the carbons and adding the ending
–ane.

For branched members, the longest chain is selected and prefix is added to the name of the
main of the chain, the position of the substituent is also indicated by appropriate number

Examples

Name the following organic compounds according IUPAC system:

(a) CH3CH2CH2CH3 (b) CH3CH2CH2CH2CH3 (c) CH3(CH2)5CH3

(d) CH3CHCH2CH3 (e) (CH3)4C (f)

CH3

Solution

(a) Butane (b) Pentane (c) Heptane (d) 2-methylbutane

(e) 2, 2-dimethylpropane (f) Cyclobutane

ISOMERISM IN ALKANES

Alkane’ s posse’ s structural isomers of class chain isomers from Butane.

Example

A hydrocarbon Q has a vapour density of 36 with empirical formula C5H12.

(a) Determine the molecular formula of Q

(b) Write down the possible isomers of Q and their IUPAC names

Soln:

(a) Molecular mass = 36x2 = 72g

(C 5 H 12 ) n  72  72n  72  n  1 M.F of Q is C5H12

(b)

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 CH3
CH3CH2CH2CH2CH3 CH3CHCH2CH3
CH3CCH3
Pentane CH3

2-methylbutane CH3
2,2-dimethylpropane

PREPARATION OF ALKANES

1. HYDROGENATION OF ALKENES AND ALKYNES

This method provides one of the most suitable methods for preparing Alkanes. It used to
deduce the number of the double or triple bond in the unsaturated hydrocarbon.

The method requires catalyst such as Nickel, Platinum or Palladium. Nickel requires an
elevated temperature of 150oC whereas Platinum and Palladium requires ordinary
temperature.

This reaction is used to determine the molecular mass of the Alkanes or Alkenes or Alkynes
based upon the stoichiometry of the reaction

Ni CnH2n+2
CnH2n + H2
o
150 C
e.g.
H2 / Ni
CH3CH CHCH3 CH3CH2CH2CH3
o
150 C

Or
Ni
CnH2n-2 + 2H2 CnH2n+2
o
150 C
e.g.
2H2 / Ni
CH3C CCH3 CH3CH2CH2CH3
o
150 C

Example

2.24dm3 of Hydrogen gas at s.t.p reacts with 8.4g of hydrocarbon Q as represented by the
equation below:

RCH CH2 + H2 RCH2CH3

(a) Identify the functional group in the hydrocarbon Q

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(b) Determine the molecular mass of Q hence that of R

(c) Write the:

(i) Molecular formula of Q

(ii) Possible isomers of Q and their IUPAC names

(1 mole of a gas occupies 22.4dm3)

Soln:

(a) Alkenes

2.24
(b) Moles of Hydrogen gas reacted =  0.1
22.4

 Moles of the Alkenes = 0.1 (since the mole ratio is 1: 1) hence the RFM = 0.1x8.4 = 84

Molecular mass of Q = 84g

 R + 2(12) + 3(1) = 84 thus R = 57g

(c) (i) From the general formula of Alkenes CnH2n

 n (12) + 2n (1) = 84 or n = 6  M.F of Q is C6 H12

(ii)

CH3CH2CH2CH2CH CH2 CH3CH2CH2CH CHCH3

Hex-1-ene Hex-2-ene

CHCH2CH3
CH3CHCH2CH CH2 and
CH3 CH2CH
Hex-3-ene
CH3 4-methylpent-1-ene
CH3

CH3CCH CH2

CH3
3,3-dimethylpropene

Page 22 of 122
2. KOLBES SYNTHESIS

When aqueous solution of sodium salt of the carboxylic acid is electrolysed, an alkane is
liberated at the anode and carbondioxide at the cathode.

This suitable for preparing symmetrical alkane of the R-R .

i.e.

2 RCOO- R-R + 2CO2 + 2e

e.g.

CH3COO- CH3CH3 + CO2 + 2e

3. DECARBOXYLATION METHOD

The sodium salt of the carboxylic acid is heated with soda lime which contains sodium
hydroxide and calcium oxide.

This reaction decreases the carbon chain by one carbon

Sodalime
RCOONa RH + Na2CO3
Heat
NaOH (s)
CH3COONa CH4
Heat

4. FROM ALKYL HALIDES

Reduction of alkyl halides also generates Alkanes. This can be done by using Zinc-Copper
couple in ethanol or using lithium aluminium hydride in dry ether.

i.e.

LiAlH4 RH +
RX LiAlX4
Dry Ether

Zn-Cu Couple
RX + 2H+ RH + Zn2+ + X-
Ethanol

e.g.
LiAlH4
CH3CH2Br CH3CH3
Dry Ether

Page 23 of 122
Hydrolysis of Grignard reagent also gives rise to alkane

Dry Ether
RX + Mg RMgX (Alkyl magnesium halide)

RMgX + H2O HCl RH + Mg(OH)X

or H2SO4
e.g.
H2O
CH3MgCl CH4
H2SO4

5. WURTZ REACTION

Haloalkanes react with metallic sodium in dry ether to yield Alkanes of higher molecular
mass and the carbons atoms are in even numbers.

Greater yield is obtained when the alkane has a higher molecular mass.

i.e.

Dry ether + 2NaX

2RX + 2 Na R-R

e.g.
CH3CH2CH2Br Na CH3CH2CH2CH2CH2CH3
Dry ether
CH3
Na
CH3CHCH3 CH3CHCHCH3
Dry ether

Br CH3

FOR METHANE

Hydrolysis of Aluminium carbide with hot water or dilute mineral acids form methane

Al4C3 + 12 HCl 3CH4 + 4AlCl3

N.B. The diagonal carbide can also be used i.e. Beryllium carbide

PHYSICAL PROPERTIES OF ALKANES

The straight chainsAlkanes, C1-C4 are gases, C5-C7 are liquids and the remaining homologues are
solids.

Page 24 of 122
Boiling and Melting points increase with increasing molecular mass although the branched
isomers are more volatile and degree of volatility increases with branching.

Alkanes are immiscible with polar solvents such as water but soluble in non-polar solvents such
as chloroform, ether etc.

Density of the Alkanes increase with molecular mass but the factor reduces with increase in the
branching.

REACTIONS OF ALKANES

Alkanes are generally unreactive compared to alkenes and alkynes.

Reasons:

 The C-C and C-H bonds are strong therefore unless heated to higher temperatures or
subjected to ultraviolet light.

 Carbon and Hydrogen have nearly the same electronegativity value therefore the bonds are
slightly polarized.

 There are no lone pairs of electrons in Alkanes therefore Alkanes are not attacked by acids.

However, under certain conditions, some of the reactions of Alkanes (paraffins) include:

1. COMBUSTION

Alkane’ s burn in excess oxygen to form carbondioxide and water,the reaction is exothermic
and it can be used to determine the molecular formula of the Alkanes.

CnH2n+2 + (3n+1)O2 nCO2 + (n+1)H2O

2. CHLORINATION OR BROMINATION

Alkanes react with halogens when heated at 250-400oC or in presence of Ultraviolet light to
form a mixture of products which are difficult to separate.

The reactivity is the order of Fluorine> Chlorine> Bromine> Iodine. Iodine does not react
with Alkanes while Fluorine reacts explosively.

Cl2
CH4 CH3Cl + CH2Cl2 + CHCl3 + CCl4
U.V.light

Mechanism

Page 25 of 122
 Cl Cl 2Cl

Cl H CH3 CH3 + HCl

H3C Cl H3CCl

N.B. The reaction mechanisms repeat to generate the rest of the products.

3. NITRATION REACTION
Alkanes react with nitric acid at about 400oC via free radical mechanism to form nitroalkane
HNO3
RH RNO2 + H2O
o
400 C

e.g.
HNO3
CH3CH2CH3 CH3CH2CH2NO2
400oC

Mechanism

HO HO + NO2
NO2

HO H CH2CH2CH3 H2O + CH2CH2CH3

CH3CH2CH2 NO2 CH3CH2CH2NO2

4. HALOGENATION USING SULPHURYL CHLORIDE

SO2Cl2 RCl + HCl + SO2

RH
40-80oC

CHAPTER THREE

ALKENES (OLEFINS)

Page 26 of 122
 Alkenes form a homologous series of unsaturated hydrocarbons containing a carbon-carbon
double bond with the general formula CnH2n .

NOMENCLATURE OF ALKENES

In accordance with the IUPAC system, an alkene is named by dropping the ending ane from
the corresponding alkane and replacing it with suffix ene.

Where required, the position of the double bond is specified by appropriate number between
the stem name and ending ene except for ethene and propene without positional isomers

Example

Name the following organic compounds using the IUPAC System:

(a) CH3CH CH2 (b) CH3CH2CH CH2 (c) CH3CH CHCH3

(f) CH3C CCH2CH2CH3

(d) CH3C CH2 (e) CH3C CHCH2CH3

CH3 CH3
CH3
CH3

Solution:

(a) Propene (b) But-1-ene (c) But-2-ene (d) 2-methylpropene

(e) 2-methylpent-2-ene (f) 2, 3-dimethylhex-2-ene

Question

(a) Draw the structure of the following organic compounds:

(i) 3, 3-dimethylcyclopentene (ii) 6-bromo-2, 3-dimethylpent-2-ene (iii) 3, 6-

dimethyloct-3-ene

(iv) 5-bromo-4-chlorohept-1-ene (v) 4-ethyl-3-methylcyclohexene

(b) Name the following organic compounds:

Page 27 of 122
 CH2CH3

(i) BrCH2CH2CH CCH3 (ii)

CH2CH2CH3
CH3 CH3

(iii) CH2CH3 (iv) CH3CH2CH CHCH2CHCH2CH3

Br

SYNTHETIC PREPARATIONS OF ALKENES

Alkenes are generally prepared by elimination of one atom or groups from two adjacent
carbon atoms mainly from alcohols and halo alkanes.

The ease of dehydration of alcohols is: 3o Alcohol> 2o>1oAlcohol while the ease of
dehydrohalogenation of halo alkanes is 3o> 2o>1o

FROM ALCOHOLS

Alcohols are heated with excess concentrated sulphuric acid or orthophosphoric acid. The
temperature of dehydration depends on the structure of the alcohol.

The reaction involves removal of water molecules hence known as dehydration reaction

The 1o and 2o Alcohols following the same mechanism while 3o Alcohols undergoes partial
ionization generating 3oCarbocations

Example

Conc.H2SO4 CH3CH CH2 + H2O

CH3CH2CH2OH o
180 C
Mechanism

+ -
CH3CH2CH2OH H OSO3H CH3CH2CH2OH2 + OSO3H

+ -H2O
CH3CH CH2 OH2 CH3CH CH2

H -
OSO3H

Page 28 of 122
Example

OH

Conc. H3PO4
+ H2O
176oC

Mechanism
+
OH2
OH
H+

+
OH2
-H2O
-H3PO4
-
H OPO3H2

Example

Conc.H2SO4
(CH3)3C OH (CH3)2C CH2 + H2O
170oC

Mechanism
+
(CH3)3CH + -
(CH3)3COH OH
-H2SO4
(CH3)2C CH2 H -
OSO3H (CH3)2C CH2

Example

Conc. H2SO4
CH3(CH2)2CH2OH CH3CH CHCH3
180oC

Write the mechanism of the above reaction.

2. FROM HALOALKANES

Halo alkanes are heated with a strong base to generate an alkene.

(i) Dehydrohalogenation of alkyl halides.

Halo alkanes are heated with a strong base such sodium amide in liquid ammonia or sodium
ethoxide in ethanol in order to remove hydrogen halide i.e.

Page 29 of 122
 EtONa / EtOH RCH CHR'
RCH2CHR'
Heat

Example

CH3CH2OK / CH3CH2OH CH3CH CH2

CH3CH2CH2Br
Heat

Mechanism
-Br-
CH3CH CH2 Br CH3CH CH2
-CH3CH2OH
H
-
OCH2CH3

Example

CH3CH2CHCH3 KOH / EtOH CH3CH CHCH3

Heat
Cl

Mechanism
KOH + EtOH EtOK + H2O

Cl
-Cl- CH3CH
CH3CH CHCH3 CHCH3
-EtOH
-
H OEt

Example

NaNH2 / Liq.NH3
(CH3)3C Br (CH3)2C CH2
Heat
Mechanism

(CH3)3C Br (CH3)3C + + Br-

-NH3
(CH3)2C CH2 H -
NH2 (CH3)2C CH2

(ii) Dehalogenation of Vicinal dihalides

Page 30 of 122
 When vicinal dihalides are heated with Zinc, alkenes are formed i.e.

Br

Zn
CH3CHCHCH3 CH3CH CHCH3
Heat
Br

N.B. On a large scale, alkenes are obtained by cracking of petroleum products

REACTIONS OF ALKENES

Alkenes undergo Electrophilic addition since they are electron rich species.

Some of the addition reactions include:

1. ADDITION OF HYDROGEN

Hydrogenation of alkenes generate alkanes

H2 / Ni
RCH CHR' RCH2CH2R'
150oC
e.g.
H2 / Ni
CH3CH CH2 CH3CH2CH3
150oC

2. ADDITION OF HALOGENS

This reaction is usually carried out in an inert solvent such carbon tetrachloride. Chlorine and
Bromine reacts but Iodine fails to react.

The reddish- brown colour of bromine is turned colourless therefore the reaction is used to
test for presence of carbon-carbon double bond and the number of double bonds since the
mole ratio is 1:1(Alkene : Bromine )

Page 31 of 122
 X2 /CCl4
RCH CHR' RCHCHR' X2 = Cl2 or Br2

X X

CCl4 CH3CHCH2Br
CH3CH CH2 + Br2

Br

Mechanism

CH3CH CH2 Br Br CH3CHCH2Br + Br-

CH3CHCH2Br CH3CHCH2Br

Br
Br

3. HALOHYDRIN FORMATION

Bromination or Chlorination of alkenes in water generates bromoalcohol or chloroalcohol

Br2 /H2O CH3CHCH2Br

CH3CH CH2

OH

Mechanism

CH3CH CH2 Br Br CH3CHCH2Br + Br-

-H+
CH3CHCH2Br CH3CHCH2Br CH3CHCH2Br

+ OH2 OH
OH2

N.B. The mechanism is the same when chlorine water is used.

4. ADDITION OF WATER / HYDRATION

Page 32 of 122
 Alkenes react with cold concentrated sulphuric acid to form alkyl hydrogen sulphate which
reacts with water on heating alcohol

H2SO4 H2O
RCH CHR' RCHCH2R' RCHCH2R'
Heat

OSO3H OH

H2SO4 H2O
CH3CH CH2 CH3CHCH3 CH3CHCH3
Heat
OSO3H OH

Mechanism

The mechanism follow markovnikov rule.

CH3CH CH2 H OSO3H CH3CHCH3 + -OSO3H

CH3CHCH3 CH3CHCH3

OSO3H
-
OSO3H

OSO3H

-
OSO3H -H+
CH3CHCH3 CH3CHCH3 CH3CHCH3

+OH2 OH
OH2

5. ADDITION OF HYDROGEN HALIDES

Hydrogen halides react with alkenes forming alkyl halides.

HX
RCH CHR' RCHCH2R' X=Cl,Br and I

In the reaction above, the hydrogen atom from hydrogen halide adds itself to the carbon
atom of the double bond with the larger number of hydrogen atoms.

Also the halogen adds itself to the carbon atom in double bond with lower number of
hydrogen atom thus these are known as Markovnikov rule.

Page 33 of 122
 HBr
CH3CH CH2 CH3CHCH3

Br

-Br-
CH3CH CH2 H Br CH3CHCH3

CH3CHCH3 CH3CHCH3

Br
Br-

Example

H3CH2C

CH2CH3
+
H Cl -Cl-

CH2CH3 CH2CH3
+

Cl
Cl-

N.B. The hydrogen bromide are usually generated by action of concentrated Sulphuric acid on
sodium bromide

6. ADDITION OF HYDROGEN BROMIDE IN PRESENCE OF PEROXIDE

In this reaction, the bromine atom adds itself to the carbon atom of the double bond having
higher number of hydrogen atoms with hydrogen atom (from Hydrogen bromide) to lower
carbon atom.

This observation is known as anti-markovnikov rule.

Page 34 of 122
 HBr
RCH CH2 RCH2CH2Br
Peroxide
e.g.
HBr
CH3CH CH2 CH3CH2CH2Br
Peroxide
Mechanism
.
RO OR 2OR
. .
RO H Br ROH + Br

CH3CH CH2 Br CH3CHCH2Br

CH3CHCH2Br + HOR CH3CH2CH2Br + OR

7. WITH ALKALINE POTASSIUM MANGANATE (VII). Manganate (VII) is a weak oxidising agent
therefore it oxidizes alkenes to diols. The purple colour turns colourless.

MnO4- / OH-
RCH CHR' RCHCHR'

OH OH

MnO4- / OH-
CH2 CH2 HOCH2CH2OH
Ethane-1,2-diol

The reaction is also used to test for unsaturated compounds. It can also occur if the reagent
is in acidic medium.

8. OZONOLYSIS

Alkenes react with ozone to form ozonide which on hydrolysis generates carbonyl
compounds.

The reaction is used to determine the structural formula of the alkene.

Alkenes with terminal double bond form methanal (HCHO), those with structure RCH= form
Aldehydes (RCHO) while those of structure RR’ C= form Ketones. i.e

Page 35 of 122
 (i) O3 /CCl4
RCH CH2 RCHO + HCHO
(ii) H2O / Zn
e.g.
(i) O3 / CCl4
CH3CH CH2 CH3CHO + HCHO
(ii) H2O / Zn

RCH CHR' (i) O3/CCl4

RCHO + R'CHO
(ii) H2O / Zn
e.g.
(i) O3 / CCl4 CH3CHO + CH3CH2CHO
CH3CH CHCH2CH3
(ii) H2O / Zn

(i) O3 / CCl4
RC CHR' RCOR" + R'CHO
(ii) H2O / Zn
R"
e.g.
(i) O3 /CCl4
CH3C CHCH2CH3 CH3COCH3 + CH3CH2CHO
(ii) H2O / Zn

CH3

N.B. Ozonolysis is the formation of ozonide followed by hydrolysis to generated carbonyl

compounds.

8. POLYMERISATION REACTION

Alkenes undergo addition polymerization to form polymers.

Ethenepolymerises to form polyethene which is an important plastic material used as

packing material.

O2 or Peroxide
n CH2 CH2 * CH2CH2 *
1500atom, 200oC
n

Sample Question

A hydrocarbon A contains 87.8% carbon. Its relative molecular mass is 82. A decolorizes bromine
and in presence of Nickel it reacts with hydrogen to form B. 0.1g of A was found to absorb
27.3cm3 of hydrogen (measured at s.t.p). B does not decolorize bromine.

(a) Determine the:

Page 36 of 122
 (i) Empirical formula

(ii) Molecular formula of A.

(b) Calculate the:

(i) Number of moles hydrogen that reacted with one mole of A

(ii) Number of double bonds in the molecule of A

(c) Write the possible Isomers of A.

CHAPTER FOUR

ALKYNES OR ACETYLENES

Alkynes are unsaturated hydrocarbons having a triple bond between carbon atoms. The
general formula of the homologous series is CnH2n-2.

NOMENCLATURE OF ALKYNES

The IUPAC names of the alkynes are obtained by taking the corresponding alkane name and
replacing the ending with suffix” –yne”.The position of the triple bond is indicated by
inserting the appropriate number between the stem and the ending”–yne”

Question:

Name the following organic compounds using the IUPAC system.

(a) HC CH (c) CH3CH2C CCH3

(b) CH3C CH (d) CH3CHC CCH2CH3

CH3

Page 37 of 122
PHYSICAL PROPERTIES

The physical properties of alkynes are similar to those of alkanes and alkenes; however they
boil at a higher temperature than alkenes and alkanes with the same number of carbon atoms
due short bond length.

Alkyne Bpt (oC) M.p.t (oC) Alkene B.p.t (oC)

Ethyne -75 -82 Ethene -104
Propyne -23 -101.5 Propene -47
But-1-yne 9 -122 But-1-ene -6.3
Hex-1-yne 72 -124 Hex-1-ene 63

Synthetic Preparation

Alkynes are usually prepared by dehydrohalogenation of dihalogencompounds.

The dihalogen compounds are heated using strong bases which include:

 Sodium ethoxide in ethanol

 Sodium amide in liquid ammonia ( solution of sodium in liquid ammonia)

 Potassium hydroxide in ethanol (contains ethoxide ions but not aqueous Potassium
hydroxide or aqueous sodium hydroxide)

KOH/ CH3CH2OH RC CR'

RCHCHR'
Heat

X X

KOH /CH3CH2OH CH3C CCH3

CH3CHCHCH3
Heat
Br Br

Mechanism

Page 38 of 122
KOH + CH3CH2OH CH3CH2OK + H2O

Br Br Br
-Br-
CH3CH CCH3
CH3C CCH3
-CH3CH2OH
H H
OCH2CH3
Br
-Br-
CH3C CCH3 CH3C CCH3
-CH3CH2OH
H
OCH2CH3

NaNH2 / Liq.NH3 CH3C CH

CH3CHCH2
Heat
Br Br

Qn: Write the mechanism of the reaction above.

Note: The dihalogen compounds are prepared by:

(a) Bromination or Chlorination of Alkenes

X2 /CCl4
RCH CHR' RCHCHR'

X X

(b)Carbonyl compounds

PCl5
CH3CH2CHO CH3CH2CHCl2

INDUSTRIAL PREPARATION OF ETHYNE

(a) Treatment of Calcium dicarbide with water

Calcium dicarbide is obtained by reducing Quicklime, obtained from Limestone, with coke in
electric furnace 2000-3000oC

Page 39 of 122
 heat CaO + CO2
CaCO3
2000oC + CO
CaO + 3C CaC2

CaC2 + 2H2O Ca(OH)2 + HC CH

(b) Partial combustion of Methane

In this method, ethyne is separated by passing the gases product through Propanoneor
Ammonia

O2 CO2 + 2H2
CH4 +
2CH4 + 3O2 2CO + 4H2O

1500oC
2CH4 HC CH + 3H2

REACTIONS OF ALKYNES

Just like Alkenes, Alkynes also undergo Electrophilic addition due to availability of loosely held
 electron. Addition of hydrogen, Halogens and Hydrogen halide to alkynes is very much like
addition to alkenes except that here two molecules of reagent can be consumed.

1. Addition of hydrogen

2H2 / Ni
RC CR' RCH2CH2R'
Heat

2. Addition of Halogens
X X

X2 / CCl4 X2 / CCl4 C R'

RC CR' RC CR' R C

X X X
X

X2 = Cl2 or Br2

Qn: Write the mechanism of the above reaction

3. Addition of Halogen halides

Page 40 of 122
 XH

HX HX RCCR'
RC CR' RC CR'

H
XH
X HX= HCl, HBr and HI

Qn: Write the mechanism of the above reaction

4. Addition of hydrogen Bromide in presence of peroxides

HBr CHBr
RCH2C CH RCH2CH
Peroxide

This reaction resemble that of alkenes to generate anti-markovnikov product

5. Addition of water. Hydration

H2O, dil.H2SO4
HC CH CH3CHO
HgSO4, o
60 C

H2O, dil.H2SO4
CH3C CH o CH3COCH3
HgSO4, 60 C

Ethyne is the only alkyne that forms Aldehydes (ethanal) while the rest form Ketones
on hydration.

6. Polymerization of Ethyne

Organo-Nickel
HC CH
60-70oC

or

Fe
HC CH
Heat

7. Substitution reaction of Acidic Hydrogen

Page 41 of 122
 Alkynes which have a triple bond at the end of the chain (terminal alkynes) have a
replaceable acidic hydrogen atom.

a) With Ammoniacal Silver nitrate Solution

Terminal Alkynes react to form white precipitate.

2 Ag+ AgC CAg + 2 H+

HC CH +
silver dicarbide
+ Ag+ RC CAg + H+
RC CH

This reagent is used to differentiate terminal alkynes from Non-terminal alkynes

b) With Ammoniacal Copper (I) Chloride solution

Terminal Alkynes react to form red precipitate

+ H2O
RC CH + Cu(NH3)2 + -OH RC CCu + 2NH3

Also, ammoniacal copper (I) chloride solution is used to differentiate terminal alkynes
from non-terminal.

c) Sodium Acetylide formation

Terminal Alkynes react with sodium in liquid ammonia to form sodium acetylide which
can be used to synthesize the higher homologue by reacting with alkyl halides.

liq. NH3 2 RC CNa + H2

RC CH + 2Na

RC CNa
R'X RC CR' + NaX

Sample Question

(a) Write equation(s) to show how the following compounds can be synthesized .In each cases
indicate the mechanism for the reactions where possible.

(i) (CH3)2C CH2 from 2-bromo-2-methylpropane

(ii) HC CH from Bromoethane

Page 42 of 122
(b) Name the reagent(s) that can be used to differentiate between the following compounds. In
each case, state what would be observed if the reagent is treated with compounds

(i) CH3CH2C CH and CH3C CCH3

(ii) CH3CH CH2 and CH3CH2CH3

When 400cm3 of the mixture of ethane and ethyne measured at room temperature was
bubbled in to mixture of aqueous ammonia and silver nitrate solution. 2.4g of a white solid
was formed.

(i) Write an equation for the reaction that took place and name the white solid

(ii) Calculate the percentage by volume of ethane in the mixture

(d) (i) Define the structural isomerism

(ii) Using suitable example(s), State the classes of structural isomerism

CHAPTER FIVE

AROMATIC HYDROCARBONS- BENZENE

Introduction

In the last chapter, we considered unsaturated compounds-Alkenes and Alkynes. There is

another important class of unsaturated compounds that needs to be considered separately
because their properties are so different from those of alkenes and alkynes.

This class of compounds is called the Aromatic hydrocarbon and its simplest member is
Benzene.

Page 43 of 122
 The name Aromatic was originally used because some derivatives of these hydrocarbons have
pleasant smells. Its is now known that just many of them have unpleasant and in any case the
aromatic vapours are toxic

Therefore the name Aromatic has been retained to indicate certain chemical characteristics
rather than odorous properties.

The structure of Benzene

Since 1834, molecular mass determination generated the molecular formula of benzene as
C6H6. The exact structural formula, however posed a problem for many years.

With such a high ratio of C: H, benzene must be a highly unsaturated with a possible structure
of hexatetraene e.g.

CH2 C CHCH C CH2

CH3C CCH2C CH

CH2 CHC CCH CH2

However, benzene does not undergo addition reactions across the double bond as alkenes
therefore Kekule (1865) proposed a ring structure in which alternate carbon atoms were joined
by double bond as:

or or

1 2 3

Bond lengths

X-ray diffraction studies show that benzene is planar and all the C-C bonds are the same.

Some of the bond lengths are:

C-C bond length in all bonds in benzene, 0.139nm

C-C bond length in cyclohexane, 0.154nm

C-C bond length in cyclohexene, 0.133nm

Page 44 of 122
 Kekule model would suggest unequal carbon-carbon lengths, alternating between double and
single bond values. In fact the constant bond length is found between single and double
bond.

Question: Explain the variation in the bond length between cyclohexane, cyclohexene and
benzene.

Soln: From Molecular orbital terms, Benzene is a planar molecular with all the six hydrogen and
six carbon atoms lying in the same plane. Each Carbon atom is sp2 hybridized and explains
why structure 3 is preferred.

Also, the variation can be attributed to resonance energy which indicates than benzene is
more stable than cyclohexene and all carbon – bond lengths in benzene are equal.

Thermochemistry of Benzene

Benzene is more stable than expected and this is illustrated using the enthalpy of
hydrogenation to cyclohexane. i.e.

The enthalpy of hydrogenation of cyclohexene is -119KJ/mol

Ni
+ H2
∆H= -119KJ/mol

Considering Benzene as Cyclohexa-1, 3, 5-triene which has three double bonds then, we expect
its enthalpy of hydrogenation to be = 3 (-119) = -357KJ/mol.

However, the experimental value observed was = -207KJ/mol.

The difference in the values (-357 + 207) = -150KJ/mol and it indicates that Benzene is more
stable than cyclohexa-1, 3, 5-triene. The difference in the values is known as Resonance or
Delocalization energy

Sources of Benzene

Benzene is obtained from petroleum oil by fractional distillation.

Synthetic Preparation

Owing to the great abundance of Benzene from Industrial sources, it is rarely prepared but
may be prepared by the following methods.

1. Decarboxylation of Sodium Salts

Page 45 of 122
 COONa

Sodalime
+ Na2CO3
Heat

2. Reduction of Phenol

OH
Zn
+ ZnO
Heat

3. Polymerization of Ethyne

Organo-Nickel Cat.
CH CH
60-70 oC

Physical properties Of Benzene

Benzene is a colourless liquid with a characteristic Aromatic smell. It is immiscible with water
but highly soluble in organic solvents as well as being used as solvent itself.

Like all Aromatic compounds, it burns with a sooty flame owing to its relatively high carbon
content

Reactions of benzene

The availability of the pie electrons in benzene serves as a source of electrons which are
donated to electron deficient species (Electrophiles). The reactions therefore are
characterized by Electrophilic substitution reactions which differ from Addition reactions of
Alkenes.

1. Nitration reaction

This is the reaction of Benzene with nitrating mixture containing equal molar quantities of
concentrated Nitric acid and sulphuric acid.

In this reaction, the hydrogen atom is substituted by a nitro group to generate Nitrobenzene.

Concentrated Sulphuric acid is used to protonate weaker Nitric acid such that
Nitroniumcation is produced.

Page 46 of 122
 NO2
Conc. HNO3
Conc. H2SO4
55-60oC

Mechanism

+ + -
HNO3 + 2 H2SO4 NO2 + H3O + 2HSO4

H
NO2 NO2
+
NO2 -H+
+

Nitrobenzene is used to produce Phenylamine (Aniline) by reduction process which is used to

manufacture azo-dyes.

An example of an azo-dye is 4-hydroxyazobenzene which is orange solid synthesized from

Nitrobenzene as shown below.

N NCl

NO2 NH2

(i) Sn/ Conc. HCl NaNO2 /Conc.HCl

(ii) Conc. NaOH (aq), Heat < 10oC

OH

N N OH
NaOH(aq)

4-Hydroxyazobenzene
(Orange solid)

2. Sulphonation reaction

This is carried out by using fuming sulphuric acid. Concentrate sulphuric acid can be used but
requires refluxing for several hours.
SO3H

Fuming H2SO4
35-50oC

Benzenesulphonic acid

Page 47 of 122
 Mechanism

+ -
2H2SO4 SO3 + H3O + HSO4

H SO3-
SO3- SO3H
O
-H+ H+
S O
+
O

N.B The overall reaction is reversible with the equilibrium tending to the left.

BenzeneSulphonic acid is used in the manufacture of phenol.i.e.

SO3H SO3Na ONa OH

NaOH (aq) NaOH H2SO4
300-350 oC

3. Halogenation

Substitution by chlorine or bromine takes place readily at room temperature in presence of

halogen carriers’ e.g iron, aluminium chloride or iodine. Iodine does not easily substitute.

The halogen carrier functions as a Lewis acid inducing a certain degree of polarity in the
halogen molecule.
Cl

Fe
+ Cl2
Heat

Chlorobenzene

Mechanism

2 Fe + 3Cl2 2FeCl3
-
+ FeCl3 Cl + FeCl4
Cl2

Page 48 of 122
 H
Cl Cl

Cl -H+

H+ + FeCl4- HCl + FeCl3

N.B. Bromine in presence of Iron (III) bromide follows the same mechanism.

Qn. Complete the reaction below, name the major product and write the acceptable
mechanism of the reaction.

FeBr3
(a) + Br2

AlCl3
(b) + Br2

4. Friedel -Crafts Alkylation

Benzene reacts with alkyl halides in presence of Aluminium halides as Lewis acid to form
alkyl benzene.
R

RX
AlX3

Example

CH2CH3
CH3CH2Br
AlBr3

Mechanism

Page 49 of 122
 AlBr3 CH3CH2 + AlBr4-
CH3CH2Br +
H
CH2CH3
CH2CH3
CH2CH3 -H+
+

H+ + AlBr4- HBr + AlBr3

The Haloalkanes can be replaced by other compounds such as Alkenes and Alcohols e.g
CH(CH3)2

+ H+
CH3CH CH2

Mechanism

CH3CH CH2 + H+ CH3CHCH3

H
CH(CH3)2 CH(CH3)2

CH(CH3)2 -H+
+

N.B. The alkyl group can be oxidized to carboxylic acid by Acidified KMnO4 or dilute nitric
acid
CH3 COOH
MnO4- /H+

Heat

5. Friedel-Crafts Acylation

Acid Halides react with Benzene in presence of Aluminium Chloride to generate Aromatic
Ketones.

COR

RCOCl
AlCl3

Example

Page 50 of 122
 COCH3

CH3COCl
AlCl3
Acetophenone

Mechanism

CH3COCl + AlCl3 COCH3 + AlCl4-

H
COCH3
COCH3
COCH3 -H+
+

N.B. Acid anhydrides i.e. (RCO)2O are generally preferred because they are easily obtained in
a state of high purity, is more easily handled and resulting Ketones is more easily separated
by distillation

Other Important Addition reactions of Benzene include:

1. with Hydrogen

Ni
+ 3H2
150oC

2. with Chlorine

Like Alkanes, Benzene undergo Addition reaction with chlorine in presence of sunlight or
Ultraviolet radiation to form 1, 2, 3, 4, 5, 6-hexacyclohexane.
Cl

Cl Cl
u.v.light
+ 3 Cl2

Cl Cl

Cl

Position of Substitution in Benzene Derivatives

When a second atom or group of atoms is attached to monosubstituted benzene, the position
of substitution is determined by the nature of the substituent already attached.

In fact, any substituent group attached to a benzene ring affects the rate and position at
which further substitution occurs.

Page 51 of 122
 The position of substitution of the second substituent is governed largely by whether or not
the atom or group already present is donating electrons to the ring or withdrawing electrons
from it.

Electron-donating groups enhance the availability of the pie electrons hence it activates the
ring generating products at position 2-(ortho) and 4-(Para).

Examples of electron-donating groups include:

NH2 NHR, NR2

R, OH, OR,

Example of substitution reaction with electron-donating group includes.

CH3 CH3 CH3

Cl
Cl2
+
AlCl3

Cl

Presence of halogens on the benzene ring deactivates the ring to products at positions 2- or 4-
on substitution.

Electron- withdrawing groups reduce the availability of the pie-electrons hence deactivate the
ring therefore on substitution position 3- preferred.

Examples of electron-withdrawing groups include:

NO2 CN CHO COR COOH and SO3H

Example includes:

Br2
FeBr3
NO2 NO2
Br

Question

(a) Complete the following reactions and in each case write the acceptable mechanism;

Page 52 of 122
 (i) Br2/FeBr3
Cold, in dark
CH3

CH3CHClCH3
(ii)
AlCl3 , Warm

(b) How would distinguish between the following members of the pairs of compounds. In each
case, state what would be observed when the reagent is treated with each member of the
series.

CH3

(i) and

(ii) and

(c) Write equation(s) to show how the following compounds can be synthesized. In each case ,
indicate the condition(s)/reagent necessary.

NO2
(i)
from

(ii) from CH3CH2OH

NH2

(iii) CH3CH(Br)CH3 from CH3CH2Br

Page 53 of 122
CHAPTER SIX

HALOHYDROCARBONS

Introduction

Organic halogen compounds are halogen derivatives of alkanes. Monohalo derivatives (Alkyl
halides) have a general molecular formula CnH2n+1 X (X= Cl, Br and I). Fluorine is excluded
because C-F bond is strong due to high electronegativity therefore C-F bond is unreactive.

Consequently fluorocarbon compounds are extremely inert and non-flammable.

Alkyl halides are divided into three classes depending on the number of the alkyl groups
attached to the carbon atom bonded to the halogen i.e.

R
RCH2X R CHX
R' C X
Primary Alkyl halide, (1o) R'
Secondary, (2o) R"
Tertiary, (3o)
CH3CH2CH2Br CH3CHCH2CH3
(CH3)3C I

Cl

Aryl halides are halogen compounds in which the halogen atom is directly attached to the
aromatic ring (Benzene). They are generally represented as ArX e.g.

NO2 CH3

Br

Cl I
H3C

If two halogen atoms are attached to adjacent carbon atom, the alkyl dihalides is known as
Vicinal Dihalides while if are attached to the same carbon then it is known as germinal
dihalides.

N.B Vinyl halides are compounds in which halogen is attached to a doubly bonded carbon e.g
chloroethene while allyl halides are unsaturated halogen compounds.

Nomenclature

Page 54 of 122
 Organic halogen compounds are named using the prefixes fluoro, chloro, bromo or iodo-.
Numbers are used to indicate the position of the halogen atom in the carbon containing
molecule.

Example

Name the following organic compounds

(a) CH3CH2Br (b) CH3CHCH2CH3 (c) (CH3)3C Cl

CH3
I
(d) C6H5CH2Cl
(e)

Soln:

(a) Bromoethane (b) 2-iodobutane (c) 2-chloro-2-methylpropane

(d) Chloromethylbenzene

(e) 4-iodomethylbenzene

Synthetic Preparation

For Alkyl halides:

1. From Alkenes

HX
RCH CHR' RCHCH2R'

(See Alkenes for mechanism and detailed position for addition product)

2. From Alcohols

SOCl2
ROH RCl + SO2 + HCl
PCl5 RCl
ROH

SOCl2
CH3CH2OH CH3CH2Cl

3. From Alkanes

Page 55 of 122
 Substitution with halogens in presence of sunlight or ultraviolet light is not suitable method
since it generates a mixture of products.

For Aryl Halides

1. From Diazonium salt

The salt is warmed with appropriate copper (I) halide e.g.

Br

CuBr / HBr
N NCl + N2
Warm

2. Direct Halogenation of Benzene

Br

Br2

FeBr3

(See Benzene for Mechanism and other halogen and Halogen carriers)

Physical Properties

Because of the polarity of the carbon-halogen bond due to electronegativity difference which
enhances dipole-dipole interaction in liquid phase, Haloalkanes have a higher boiling point
than alkanes of comparable molecular mass.

Most Haloalkanes are liquids (except Iodomethane) and their boiling points depend on the
alkyl group and halogen atom. Fluoroethane and chloroethane are gases.

For corresponding halogen atoms, boiling points increases with increasing molecular mass.
Densities decreases in the same order due to close packing of smaller molecules in the liquid
phase.

Haloalkanes and Aryl halides are both insoluble in water but soluble in organic solvent due to
inability to form hydrogen bonds with water.

Reactions

The Haloalkanes are fairly reactive compounds due to polarity of the Carbon-halogen bonds
therefore the electron deficient carbon atom is susceptible to attack by electron rich species
hence their reactions are characterized by Nucleophilic substitution reactions.

Some of the Nucleophilic substitution reactions include:

Page 56 of 122
1. Ether Formation

This reaction provides the suitable method for preparation of alkoaromatics and
alkoalkanes.

- +
CH3CH2ONa
CH3CH2Br CH3CH2OCH2CH3
ethoxyethane

Mechanism

CH3CH2 Br -Br-
CH3CH2OCH2CH3

-
OCHCH3

CH3CH2O-Na+ (CH3)2CHOCH2CH3
(CH3)2CH Br

CH3CH2I + O-Na+ OCH2CH3

Write the mechanism for the above reactions.

N.B. Sodium or Potassium Alkoxideare prepared by dissolving alkali metal in the excess
appropriate alcohol.

2. Ester Formation

If the haloalkane is warmed with alcoholic solution of silver salt of carboxylic acid, an ester
(sweet fruity smell) is formed. Silver halide is precipitated.

CH3COO-Ag+/ ethanol
CH3CH2Br CH3COOCH2CH3
warm
ethylethanoate

Mechanism

CH3CH2 Br -Br-
CH3COOCH2CH3

OOCCH3

Page 57 of 122
The reaction cannot be used to generate phenyl esters.

N.B. A solution of Silver ethanoate in ethanol can be used to distinguish Haloalkanes from Acryl
halides.

3. Amine Formation

When concentrated Ammonia solution is heated when Haloalkane in a sealed tube, different
classes of amines are generated.

NH3
CH3CH2Br CH3CH2NH2
Heat in sealed tube

CH3CH2NH2 + CH3CH2Br CH3CH2NHCH2CH3

(CH3CH2)3N
(CH3CH2)2NH + CH3CH2Br

To generate Primary amine, excess ammonia is used.

The reaction is limited to haloalkanes although aryl halides react if electron-withdrawing

groups are present in 2- or 4- positions.

4. Cyanide (Nitrile) Formation

When heated, haloalkanes react with potassium cyanide in an alcohol to generate

alkanenitrile.

KCN/ EtOH
RX RCN + KX
heat

Example

KCN /EtOH
CH3CH2Br CH3CH2CN
Heat

Mechanism

CH3CH2 Br -Br-
CH3CH2CN

CN

Page 58 of 122
Aromatic nitriles are not prepared from aryl halides but from benzene Diazonium salts. i.e

CN
NaNO2 /Conc.HCl CuCN
NH2 N NCl
< 10oC

Alkanenitrile are usually used to generate carboxylic acid of higher carbon chain. i.e.

H2O /H+ RCOOH

RCN
reflux

Example

KCN / EtOH H2O /H+

CH3Br CH3CN CH3COOH
heat reflux

5. Higher Alkyne formation

Haloalkanes react with sodium salt of acidic alkyne to form higher non-terminal alkynes.

R'X + RC C-Na+ RC CR' + NaX

6. Grignard Reagent Formation.

Both haloalkanes and Aryl halides react with Magnesium in presence of dry ether to
generate Grignard reagent.

Mg R'MgX
R'X
dry ether Alkyl magnesium halide

The reagent is widely used to generate alkanes, alkenes, alkynes, alcohols, Aldehydes,
Ketones and carboxylic acid.

For Alkanes:

Mg H2O
R'MgX R'H + MgXOH
R'X dil.HCl
dry ether Alkane

For Alcohols:

H2O
dry ether RCH2OMgX RCH2OH
RMgX + HCHO dil. HCl
(methanal) (1oAlcohol)

Page 59 of 122
Example:

Cr2O72- /H+ CH3CH2MgBr

CH3OH HCHO CH3CH2CH2OMgBr
dry ether
Heat
H2O
CH3CH2CH2OH
dil.HCl

RMgX H2O
R'CHO RCHR' RCHR'
dry ether dil.HCl
(Not HCHO)
OH
OMgX
(20Alcohol)

Example

Write equations showing how Propene can be converted to Butan-2-ol.

Sol:
HBr NaOH (aq) CH3CH2CH2OH
CH3CH CH2 CH3CH2CH2Br
Peroxide Heat

Cr2O72-/H+ heat

H2O CH3MgBr
CH3CH2CHCH3 CH3CH2CHCH3 CH3CH2CHO
dil HCl dry ether

OH OMgBr

Example

R" R"
R"MgX H2O
RCOR' R C R' R C R'
dry ether NH4+ (aq)
(ketone) OMgX OH
(3oAlcohol)

N.B. Aqueous Ammonium salt is used in hydrolysis to generate 3 oAlcohol because the acid may
dehydration to form Alkene.

Qn: Write equations showing how 2-methylpropan-2-ol can be synthesized from propan-2-ol.

For Ketones

Page 60 of 122
 R'MgX 2H2O RCOR'
RCN R C NMgX
dry ether dil.HCl
(Not CH3CN)
R'

For Carboxylic Acid

dry ether H2O RCOOH + Mg(OH)X

RMgX + CO2 RCOOMgX
dil.HCl (Carboxylic acid)

Example

Write equations showing how Benzoic acid can be prepared from Bromobenzene
MgBr COOMgBr
Br
Mg Solid CO2
dry ether OR dry ice

H2O dil.HCl

COOH

7. Alcohol Formation

On heating, Alkyl halides react with sodium hydroxide solution on heating to form an
alcohol.

For 3o Alkyl halide, the kinetic studies show that it is First order with respect to the alkyl
halides consequently the rate determining step involves only the haloalkane therefore the
mechanism and reaction is known as Substitution Nucleophilicunimolecular (SN1)

NaOH (aq) (CH3)3C OH

(CH3)3C Br
Heat

Mechanism

(CH3)3C Br (CH3)3C+ + Br-

(CH3)3C+ + OH- (CH3)3C OH

Page 61 of 122
Qn: Draw a well labelled energy profile diagram for the reaction and State rate law for the
reaction above.

For 1ohaloalkane alkaline hydrolysis, the kinetic studies show that it is second order reaction
therefore the dependent on the concentration of Haloalkane and hydroxide ions.

Consequently the rate determining step involves both species therefore the mechanism and
reaction is known as Substitution Nucleophilic bimolecular (SN2)

NaOH (aq)
CH3CH2Br CH3CH2OH
heat

Mechanism
CH3

Slow step Fast

CH3CH2 Br Br C OH CH3CH2OH + Br-
rate determining step

- OH H
H
Activated complex
Qn: Draw a well labelled energy profile diagram for the reaction and State rate law for the
reaction above.

Secondary haloalkanes show a mixture of both second and first order kinetics with the former
predominating.

8. Alkene Formation or Elimination reaction

The reaction involves removal of halide ion and hydrogen to form the alkene. The hydrogen
atom removed is the one bonded to the carbon atom adjacent to the one bonded to the
halogen.

Unimolecular elimination (E1)

This is undergone by 3ohaloalkane to generate an alkene in presence of alcoholic potassium

hydroxide and heat.

KOH/ EtOH
(CH3)3C Br (CH3)2C CH2
heat

Qn: Write the mechanism for the reaction

Bimolecular Elimination (E2). This is undergone by 1ohaloalkane and in the rate determining
involves both the haloalkane and base to generate the alkene.

Page 62 of 122
 KOH/ CH3CH2OH
CH3CH2CH2Br CH3CH CH2
Heat

Qn: Write the mechanism for the reaction.

9. Reduction reaction

This can be done by:

(a) Using Lithium Aluminium hydride in dry ether.

LiAlH4
RX RH
dry ether

(b)Using sodium metal in dry ether (Wurtz reaction)

Na R-R
RX
dry ether

ELECTROPHILIC SUBSTITUTION REACTION OF ARYL HALIDES

Aryl halides differ in reaction from haloalkanes in that they do not undergo substitution of the
halogen. This is because the lone pair of electrons on the halogen atom interacts with the
delocalized electrons of the benzene ring. This strengthens the carbon-halogen bond or makes
the carbon-halogen partly double bonded and difficult to break.

In the Alkyl halides, the carbon-halogen bond is polar because the halogen is a more
electronegative atom therefore the carbon atom becomes partial positively charged atom. It is
then attacked by electron rich species (Nucleophile) leading to substitution of the halogen
atom.

Generally Aryl halides undergo Electrophilic substitution reaction to generate ortho and Para
products.

Some of the reactions include:

Page 63 of 122
 Br Br

NO2

Conc HNO3
Br +
Conc.H2SO4
60oC

Br NO2

SO3H Br

Fuming H2SO4
+
SO3H

Reagents used to distinguish Aryl halides from Alkyl halides include:

Hot silver ethanoate in ethanol or hot sodium hydroxide solution and silver nitrate solution

Sample Question:

1. Suggest Explanations for each of the following observations:

a) Iodobenzene is more reactive than chlorobenzene towards but much less reactive than
iodoethane.

b) Tetrachloromethane is much less reactive towards Nucleophiles than chloromethane

c) Iodo-and Bromo-compounds are much more useful as intermediates in synthesis than

chloro-compounds.

2. Using equations indicating the required conditions to show how the following compounds
can be synthesized:

CH2 CH2 to CH3CH2COOH

a)
to CH3OCH2CH2OCH3
b) CH2 CH2

C6H5CH2OH
c) C6H5CH3 to

to
d) CH3CH2Br CH3CH2CH2OH

3. (a) Methyl Benzene reacts with chlorine to form Chloromethylbenzene. State the conditions
for the reaction

(b) Under different conditions the product is phenyl chloromethane instead of

Chloromethylbenzene.

(i) State these conditions of the reaction (ii) Write a plausible mechanism for the reaction.
Page 64 of 122
CHAPTER SEVEN

ALCOHOLS OR ALKANOLS AND PHENOL

Introduction

Aliphatic Monohydric Alcohols are monohydroxyl derivatives of alkanes and have a general
formula CnH2n+1OH or Cn H2n+2O

Aliphatic monools may be classified as 1o,2o or 3o according to the nature of the carbon atom to
which the hydroxyl group is attached i.e.

CH3

CH3CH2OH CH3CHCH3 CH3C CH3

OH
1o 3o
2 o OH

Aromatic Alcohols have aryl group attached to aliphatic portion of the alcohol separated by at
least a methylene group. E.g

CH2CH2OH CH2OH

2-Phenylethanol Phenylmethanol

Compounds in which the hydroxyl group is attached directly to the benzene (Aromatic)ring are
classified as Phenol. E.g
OH COOH

OH

Phenol
OH
2-Napthol
p-Hydroxybenzoic acid

Page 65 of 122
Alcohols containing two hydroxyl groups are described as dihydric alcohols or diols and those
with three hydroxyl groups are triols while those containing many hydroxyl groups are polyols.
E.g.

CHO
HOCH2CH2OH HOCH2CHCH2OH
HOHC
Ethane-1,2-diol OH
CHOH Glucose
Propane-1,2,3-triol
HOHC
CHOH

CH2OH

NOMENCLATURE OF ALCOHOLS

The IUPAC Names are obtained by dropping the ending “–e “of alkane and replacing it with
suffix “-ol”. The position of the hydroxyl group is indicated by inserting an appropriate number
between the stem name and ol.

Example:

Name the following compounds using the IUPAC System

(a) CH3OH (b) CH3CH2OH (c) CH3CH2CH2OH (d) (CH3)3CCH2OH

CH3CHCH2Br
OH
(e) OH (f) CH3CH2CH(CH3)CH2OH (g) OH (h)

Solution

(a) Methanol (b) Ethanol (c) Propan-1-ol (d) 2,2-dimethylpropan-1-ol

(e) 1-bromopropan-2-ol (f) 2-methylbutan-1-ol (g) Cyclohexanol (h) Cyclopropanol

ISOMERISM

Aliphatic monools have structural isomers .i.e. Chain, functional and Positional Isomers.

Ethers are functional isomers of monools.

Example:

Page 66 of 122
A compound X has molecular formula C3H8O. Write down the structural formulae and names of
the possible isomers of X.

Solution:

CH3CH2CH2OH CH3CHCH3 CH3OCH2CH3

Propan-1-ol
OH
Propan-2-ol Methoxyethane

SYNTHETIC PREPARATION OF ALCOHOLS

1. From Alkenes

conc. H2SO4 H2O

RCH CHR' RCHCH2R' RCHCH2R'
Heat

OSO3H OH

conc.H2SO4 H2O
CH2 CH2 CH3CH2OSO3H CH3CH2OH
Heat

2. From Alkyl halides

NaOH (aq)
RX ROH + NaX
heat

NaOH (aq)
CH3CH2Br CH3CH2OH
Heat

3. From Carbonyl compounds

Reduction of carbonyl compounds generates alcohol. Aldehydes are reduced to Primary

Alcohol while Ketones to Secondary Alcohol.

The reducing agents commonly used are Na/ethanol, LiAlH4 in dry ether, NaBH4 and
water, amalgamated Zinc and concentrated Hydrochloric acid, finely divided Ni or Pt
with hydrogen gas.

Lithium Aluminium hydride does reduce a double bond if it is present in the carbonyl
compound.

Page 67 of 122
 LiAlH4
CH3CH2CHO dry ether CH3CH2CH2OH

LiAlH4 H
O
dry ether
OH

4. Grignard Reagent Synthesis

See Reactions of Haloalkanes.

5. Reduction Of Carboxylic acids

Carboxylic acids are reduced to Primary Alcohols using LiAlH4 in dry ether.

LiAlH4
RCOOH RCH2OH
dry ether
LiAlH4
CH3CH2COOH CH3CH2CH2OH
dry ether

6. From Esters

Esters are hydrolysed by aqueous sodium hydroxide solution to generate an alcohol.

However this is not usually done since esters are obtained from alcohols.

OH-(aq)
RCO2R' RCOO-(aq) + R'OH
heat

7. Cannizzaro Reaction

Aromatic Aldehydes without  -hydrogen atoms undergo self-reduction and oxidation

in sodium hydroxide solution.

2C6H5CHO + NaOH C6H5COONa + C6H5CH2OH

DOMESTIC PRODUCTION OF ETHANOL

Ethanol is mainly prepared by fermentation process. Fermentation is a process where starch or

sugar is converted to ethanol by yeast enzymes.

The main sources of the starch materials include maize, millet, cassava, sorghum, potatoes,
banana, rice, molasses, etc.

The enzymes that participate in the fermentation process and their stages include:

Page 68 of 122
 Diastase
2(C6H10O5)n + n H2O n C12H22O11
Starch Maltose

C12H22O11 + H2O Maltase 2C6H12O6

Maltose Glucose

Zymase 2CH3CH2OH + 2CO2

C6H12O6

Qn:

a) Describe the processes involved in the production of ethanol from a named material
domestically

b) State briefly how the purification of the ethanol produced can be done

c) State four uses of ethanol

d) State two effects of over consumption of ethanol on the human body.

Physical Properties of Alcohols

a) Solubility
Lower members of the series are soluble however, solubility decreases as the hydrocarbon
portion increases. The miscibility of alcohols is due to ability of the formation of hydrogen bond
with water molecule.

b) Boiling Points

Alcohols boil at higher temperatures expected because the molecules associate through
hydrogen bonding which requires an extra energy to break.

Within the series, boiling points increase with molecular mass.

c) Density

Density increases with increasing molecular mass although branching reduces the factor.
Aliphatic alcohols are less dense than water while Aromatic alcohols tend to be slightly denser
than water.

REACTIONS OF ALCOHOLS

1. With Electropositive Metals

Page 69 of 122
 Although Alcohols are neutral to neutralization indicators, the hydroxyl group can be replaced
by metals of Group I and II of the periodic table. The products are hydrogen gas and metal
Alkoxide.

2ROH + Na 2RO-Na+ + H2
Na CH3CH2O-Na+
CH3CH2OH + H2

2. Halogenation

This can be done by:

a) Using Hydrogen Halide

They react with hydrogen halides to form alkyl halides. The order of reactivity for alcohols is
3o>2o>1o while for hydrogen halides is HI>HBr>HCl.

HX
ROH RX + H2O

1o Alcohols undergo bromination with hydrogen bromide which is generated from sodium
bromide and concentrated sulphuric acid.

In case of hydrogen chloride, the reaction is carried by using anhydrous Zinc chloride and
concentrated hydrochloric acid. (Luca’ s Reagent)

The reagent is used to distinguish the classes of monools i.e.

 30 Alcohol forms a cloudy solution immediately

 2oAlcohols forms cloudiness between 5-10minutes

 1o Alcohol no observable change.

Mechanism

+
ROH H X ROH2 + X-

R OH2 RX + H2O

:X-

Page 70 of 122
b) Using Phosphorous Halides

PX3
ROH RX + H3PO3 where X= Br or I

c) Using Thionyl chloride

Thionyl Chloride and Phosphorous pentachloride generate alkyl chloride.

ROH + PCl5 RCl + POCl3 + HCl

ROH + SOCl2 RCl + SO2 + HCl

3. Concentrated Sulphuric acid

The products of the reaction depend on the conditions of the reaction under which it is carried
out.

a) At lower temperatures (below 140oC), alkyl hydrogen sulphate is obtained

Conc. H2SO4
ROH ROSO3H + H2O

Conc.H2SO4
CH3CH2OH CH3CH2OSO3H + H2O

(ethyl hydrogen sulphate)

Mechanism

+ -
CH3CH2OH H OSO3H CH3CH2OH2 + OSO3H

+
CH3CH2 OH2 CH3CH2OSO3H + H2O

-
OSO3H

b) At about 140oC when excess alcohol, ether is obtained.

Conc. H2SO4
ROH ROR + H2O
140oC

Page 71 of 122
 Conc.H2SO4
CH3CH2OH CH3CH2OCH2CH3
o
140 C

Mechanism

+ -
CH3CH2OH H OSO3H CH3CH2OH2 + OSO3H

+ -H2O + -H+
CH3CH2 OH2 CH3CH2OCH2CH3 CH3CH2OCH2CH3

H
HOCH2CH3

c) When the reaction is carried out at about 180oC, an alkene is obtained. Aluminium
Oxide at 350oC or concentrated orthophosphoric acid can be used.

Conc. H2SO4 RCH CHR' + H2O

RCHCH2R'
180oC
OH

Conc.H2SO4 CH2 CH2

CH3CH2OH
Heat

4. Oxidation reaction

The product oxidation depends on the type of alcohol and partly the power of oxidizing
agent.

Primary Alcohols are oxidized to Aldehydes and the reaction proceeds to carboxylic acid
while Secondary Alcohols are oxidized to Ketones.

Tertiary Alcohols are resistant to oxidation.

The oxidizing agents commonly used are acidified potassium dichromate or acidified
chromium (VI) oxide

Cr2O7 2-/ H+ Cr2O72-/H+

RCH2OH RCHO RCOOH
Heat Heat
Aldehyde carboxylic acid
2- +
Cr2O7 /H RCOR'
RCHR'
Heat Ketone
OH

Page 72 of 122
5. Esterification reaction

The process whereby a primary alcohol reacts with a monocarboxylic acid is known as
esterification.

The reaction usually takes place in presence of concentrated sulphuric acid and it is
reversible reaction.

RCOOH + R'OH RCOOR' + H2O

Example:

CH3CO2H + CH3OH CH3CO2CH3 + H2O

Mechanism:

This was determined using radioactive Oxygen (18). The primary alcohol containing
oxygen-18 is reacted with monocarboxylic acid. The mass spectrometer is used to
analyse the ester and water formed. The oxygen-18 is found in the ester only and not
water indicating that carbon-oxygen single bond in the acid and oxygen-hydrogen bond
in the alcohol are bonded.

OH
+
O O H
CH3C + H+ CH3C CH3C OH

OH OH
+O CH3
O CH3
H
H

H+ shift

+
OH +OH2
-H+ -H2O
CH3COOCH3 CH3C CH3C OH

OCH3
OCH3

6. Iodoform reaction

Page 73 of 122
 H

CH3C R

Alcohols of the form OH react with iodine in presence of sodium hydroxide

solution to form a yellow solid.

Iodine is an oxidizing agent and can oxidize alcohols to Aldehydes or Ketones.

RCHCH3 + OI- RCOCH3 + H2O + I-

OH

OR

RCHCH3 + I2 + 2OH- RCOCH3 + H2O + I-

OH

Ethanol is the only primary alcohol which gives a positive.

N.B. Chlorine forms chloroform which is colourless liquid, Bromine forms bromoform
which is reddish-brown.

PHENOL

Introduction

These are compounds containing a hydroxyl group attached directly to aromatic nucleus
(Benzene) and have a general formula ArOH.

Like alcohols they may be monools or polyols depending on the number of the hydroxyl groups
they contain.

Examples include:
OH

OH CH3

Phenol 4-Methylphenol

Physical Properties

Page 74 of 122
Phenol is colourless crystalline solid although often found red tint due to presence of oxidation
products. It is slightly soluble but very soluble in organic solvents.

N.B. The introduction of the hydroxyl group into an already substituted aromatic ring especially
in position-4 produces a marked increase in the boiling point. E.g. the greater volatility of 2-
nitrophenol is attributed to intramolecular hydrogen bonding while the higher boiling points of
3- and 4- isomers are direct result of intermolecular hydrogen bonding.

Preparation of Phenol

a) From Benzene sulphonic acid

SO3H SO3Na O-Na+

Fuming H2SO4 NaOH NaOH

300-350 OC

H2SO4

OH

b) From Benzene Diazonium salt.

N NCl- OH

H2O

Warm

c) Cumene process

CH3
CH(CH3)2 C OOH
CH3CH CH2 O2 CH3
AlCl3

OH

CH3COCH3 + H2SO4

Reactions of Phenol

Phenol undergoes two distinct reactions i.e.

Page 75 of 122
a) Side-chain substitution reactions which generally involves replacement of the acidic
proton

b) Electrophilic substitution in the ring.

Phenol as an acid

Phenol is a stronger acid than alcohols but weaker acid compared to carboxylic acid.

Qn: Explain briefly why phenol is more acidic compared to Ethanol

Soln: In phenol, the lone pair of electrons on the oxygen atom interacts with delocalized
electrons of the benzene ring. This strengthens the carbon-hydrogen bond while
weakening the oxygen-hydrogen bond consequently; phenol loses a proton easily
making it acidic.

OH O-

(aq) + H+ (aq)
(aq)

In ethanol, the oxygen-hydrogen bond is not weakened and the proton is not easily lost.
This is because there are no delocalized electrons to interact with lone pairs of electrons
on the electrons.

Note: Due to the above reason, phenol differs from alcohols in that it does not react with
halogen acids or Phosphorus halides and does not undergo elimination reaction

a) Side-chain reactions include:

1) Esterification reaction

Phenol reacts with acid chlorides and acid anhydrides to form esters

OH + CH3COCl OCOCH3 + HCl

Phenylethanoate

2) Ether Formation

Sodium phenate (Sodium phenoxide) reacts with alkyl halides to form ethers

Page 76 of 122
 NaOH (aq) O-Na+
RX OR
OH

3) With Neutral Iron (III)chloride solution

Phenol reacts with neutral Iron (III) chloride solution to form a violet colouration due
to a complex formed.

b) Electrophilic Substitution of the ring

Phenol is more reactive towards Electrophilic reagent than Benzene since it activates
position 2- and 4- therefore the products formed at those positions.

1) Reduction reaction

Ni OH
OH + H2 Heat

2) Nitration reaction
OH OH
OH NO2
Dil.HNO3 +

NO2

3) Bromination

In aqueous solution, phenol reacts with bromine to form a white precipitate of 2, 4,

6-tribromophenol.

This reaction is used also to test for presence of phenol and estimate phenol
quantitatively.

OH OH
Br Br

+ 3Br2 + 3HBr

Br

4) Coupling with Benzene Diazonium salts

Page 77 of 122
 Benzene Diazonium salt solution is added to alkaline solution of phenol to generate
bright yellow precipitate of 4-hydroxyphenylazobenzene.

+ OH-
N N + OH N N OH

4-hydroxphenylazobenzene

Question

1. Explain the following observation:

a) Ethanol is more acidic than 2-methylpropan-2-ol but less acidic than phenol

b) Phenol is easily nitrated using nitric acid whereas Benzene is nitrated using a mixture
of concentrated nitric acid and sulphuric acid

c) Butan-1-ol is more soluble in 5M hydrochloric acid than in water

d) The boiling point of ethanol (78oC) is greater than Ethoxyethane (35oC)

2. Write the half and overall equation of reaction for:

a) Ethanol and acidified potassium dichromate solution

b) Ethene and acidified potassium manganate (VII) solution

Page 78 of 122
 CHAPTER EIGHT

CARBONYL COMPOUNDS

Introduction

Aldehydes and Ketones are referred to as Carbonyl compounds as both contain the carbonyl
functional group.

The saturated aliphatic series are homologous and correspond to a general molecular formula
CnH2nO.

Aldehydes possess single hydrogen attached to the carbonyl carbon whereas Ketones always
contain two hydrocarbon groups

Aldehydes are more reactive therefore easily oxidized and also more susceptible to Nucleophilic
addition.

Nomenclature of Aldehydes and Ketones

For Aldehydes, the IUPAC names are obtained by dropping the ending “-e”of the corresponding
alkane and replacing it with suffix “-al” for Aldehydes name.

The IUPAC names for Ketones is also obtained by dropping the ending”-e” of alkanes and
replacing it with suffix”-one”

The position for carbonyl group is indicated by inserting an appropriate number between stem
name and –one.

Example

Name the following organic compounds:

(a) CH3CH2CHO

(b) CH3CHCH2CHO

CH3
(c) CH3COCH2CH2CH3

Page 79 of 122
 PHYSICAL PROPERTIES OF CARBONYL COMPOUNDS

Simple aliphatic Aldehydes and Ketones with exception of methanal are all colourless liquids.
The lower Aldehydes possess rather unpleasant smell whereas Ketones and
Benzenecarbaldehyde have pleasant, sweet odours.

Methanal is a gas at room temperature and rest are liquids. Carbonyl group is polar therefore
Aldehydes and Ketones have a higher boiling points but lower than those of alcohols since they
do not form strong hydrogen bonds with each other.

Lower Aldehydes and Ketones are appreciably soluble in water due to their ability to form
hydrogen bonds with water molecules and the resultant solution is neutral to litmus.

The density of the aliphatic compounds of both series is less than that of water but it increases
with increase in molecular mass.

Synthetic Preparations

1) Oxidation of Alcohols

1o Alcohols are oxidized to Aldehydes while 2o Alcohols are oxidized to Ketones using acidified
potassium dichromate or acidified chromium (VI) oxide.

Cr2O72-/ H+ Cr2O72-/ H+
CH3CH2OH CH3CHO CH3COOH
Heat ethanal Heat ethanoic acid
ethanol

Cr2O72-/ H+
(CH3)2CHOH (CH3)2CO
Heat
Propan-2-ol propanone

Oxidization can also be accomplished by dehydrogenation of the alcohol using copper catalyst
heated at about 300oC

Cu
RCH2OH RCHO
o
300 c

2) From Grignard reagent.

When Grignard reagent reacts with cyanide compounds and on hydrolysis a Ketones are
obtained.

Page 80 of 122
 RMgBr 2H2O RCOR' + MgBrOH + NH3
R'CN RC NMgBr
dry ether dil.HCl
R'

3) Decarboxylation method of Calcium salts

heat
(CH3COO)2Ca + (HCOO)2Ca 2CH3CHO + 2CaCO3

heat
(CH3COO)2Ca CH3COCH3 + CaCO3

4) Ozonolysis of Alkenes

R R"
(i) O3/CCl4
C C RCOR' + R''COR'''
(ii) H2O/ Zn
R' R'''

(i) O3 /CCl4 CH3CHO

CH3CH CHCH3
(ii) H2O/ Zn

5) Hydration of Alkynes

H2O, dil. H2SO4

RC CR' RCOCH2R'
o
HgSO4, 60 C

H2O, dil.H2SO4
CH CH CH3CHO
HgSO4 , 60oC

6) From methyl benzene

CrO2Cl2 CHO
CH3

methylbenzene benzylaldehyde

QN: Show methyl benzene can be converted to Benzoic acid using equation (s) of reactions.

7) Acylation method

RCOCl
COR
AlCl3

Question:
Page 81 of 122
a) Write the mechanism of the reaction above

b) Using equations show how 1-phenyl ethanol can be prepared from benzene.

c) Write equations showing how Benzene can be obtained from 1-phenylethanol.

Reactions of Carbonyl compounds

In carbonyl compounds, the carbonyl carbon has a partial positive charge because it is bonded
to a more electronegative oxygen atom therefore it is attacked by a Nucleophile.

The susceptibility of the carbonyl carbon to Nucleophilic attack is reduced by its attachment to
electron-releasing alkyl or aryl groups which reduces the degree of positive charge on the
carbon.

Steric hindrance by the hydrocarbon groups impedes the approach of the attacking Nucleophile
and reduces the reactivity.

Some of the Nucleophilic addition reactions include;

1) Addition of Hydrogen cyanide:

R'
HCN
RCOR' R C CN

OH

HCN H
RCHO R C CN

OH

Hydrogen cyanide is usually prepared during a reaction of dilute sulphuric acid on alkali metal
cyanide.

OH
HCN
CH3CHO CH3C CN

Mechanism

Page 82 of 122
 OH
OH
+
H
CH3CHO CH3C H CH3CHCN

CN

Cyanohydrins are used to synthesize 2-or  -hydroxy acids on hydrolysis.

H2O / H+
RCHCN RCHCOOH
reflux
OH OH

Qn: Using equations indicating the necessary conditions show Ethene can be converted to 2-
hydroxypropanoic acid.

2) Addition of saturated sodium hydrogen sulphite solution

The reaction occurs readily with most Aldehydes and some Ketones especially methyl
Ketones to form white solids of Aldehydes or Ketones hydrogen sulphite.

R OH
R
NaHSO3 C
C O
R' R' SO3Na

Aldehyde or Ketone hydrogen sulphite

OH
NaHSO3
CH3CHO CH3C SO3Na

Mechanism

O-
OH
+
CH3C H H Na+
CH3CH O CH3C H CH3CHSO3Na
shift
O S O OH
O SO3-
OH
S O-

OH

Page 83 of 122
 Qn: Write equation showing show Propanone can be converted to Propanone hydrogen
sulphite and indicate the mechanism of the reaction.

3. Condensation reaction or Elimination of water molecules.

In this reaction, carbonyl compounds react with derivatives of ammonia of general form X-
NH2 to release water molecules.

The final products are usually solids which are easily isolated and purified by
recrystallisation.

Some of the addition reagents include:

a) With Hydroxylamine,NH2OH

The product formed is white solid is Aldehydes or Ketone oxime.

NH2OH
RCOR' RC NOH + H2O
R'

NH2OH CH3CH NOH + H2O

CH3CHO
ethanal oxime

Qn: Write the mechanism of the reaction above and show how the product formed can
be converted to:

(i) CH3CH2NH2

(ii) CH3COOH

b) With hydrazine, NH2NH2

The product is Aldehydes or Ketoneshydrazone which in excess yield azine.

NH2NH2 RCHO RCH NN CHR + H2O

RCHO RCH NNH2

+ H2O

Mechanism

Page 84 of 122
 H O-
H+ OH- +
RC O RC H RCH OH RCH NHNH2
shift
+ NH2NH2 NHNH2 -H+
NH2NH2
RCH NNH2

N.B. In presence of an acid, protonation is the first stage

+ OH
+
H RC H
RCHO

c) With Phenyl hydrazine C6H5NHNH2

Carbonyl compounds generate phenyl hydrazone derivatives which are low melting point
solids. The reaction occurs with or without an acid.

OH
OH
H+ RC NH2N
RCOR' RC R'
R'

H+ shift
NH2NH

+ OH2
-H2O NHN
RC NHN RC

R' R'

-H+

H
RC N N

R'

d) With 2,4-dinitrophenylhydrazine

2,4-dinitrophenylhydrazine is utilized in Brady’ s reagent for detection of a carbonyl

functional group. Yellow or orange solid crystallizes out in the form of 2,4-
dinitrophenylhydrazone.

Page 85 of 122
 H+
RC NN + H2O
RCOR' + NH2NH
H
NO2 R'

Aldehyde or Ketone
2,4-dinitrophenylhydrazone

NO2

e) With semicarbazide, NH2NHCONH2

RCOR' + H2NNHCONH2 RC NNHCONH2 + H2O

R'
semicarbazone

4. Reaction with Primary amines.

Aldehydes react with primary amines to form imines.

RCHO + H2NR' RCH NR' + H2O

C6H5CH2NH2
CH3CHO CH3CH NCH2C6H5 + H2O

5. Aldol condensation

Aldehydes react with alkali to generate Aldol product which dimerises on warming to enal.

The reaction is undergone by carbonyl compounds with at least one-α-hydrogen atom.

OH- (aq) warm

CH3CHCH2CHO CH3CH CHCHO + H2O
CH3CHO
OH
OH- (aq) warm
CH3COCH3 (CH3)2C CH2COCH3 (CH3)2C CHCOCH3

OH

6. Cannizzaro reaction

Aldehydes without at least one-α-hydrogen atom react with sodium hydroxide solution
to undergo self-oxidation and reduction reaction.

This reaction is limited to aromatic and aliphatic compounds in which the carbonyl
carbon is attached to tertiary alkyl carbon atom.

Page 86 of 122
 reduction

2C6H5CHO C6H5COONa + C6H5CH2OH

oxidation

7. Oxidation reaction

Aldehydes are oxidized to carboxylic acids by oxidising agents such as acidified

potassium dichromate solution, acidified chromium (VI) oxide solution or dilute nitric
acid.

Ketones are resistant to oxidation by common oxidising agents.

Cr2O72- /H+
RCHO RCOOH
heat

8. Reduction reaction

Aldehydes are reduced to Primary alcohol while Ketones are reduced to Secondary
Alcohol.

Reducing agents commonly used are LiAlH4/ dry ether, Hydrogen /Nickel at 150OC,
Amalgamated Zinc and concentrated hydrochloric acid, NaBH4/ Water.

LiAlH4
RCHO RCH2OH
dry ether
Aldehyde 1o Alcohol
LiAH4 RCHR'
RCOR'
Ketone dry ether OH

9. Halo form reaction

Ethanal and Methyl Ketones react with iodine in presence of sodium hydroxide solution
to form a yellow solid.

RCOCH3 + 3I2 + 4NaOH RCOONa + 3H2O + CHI3 (s) + 3I-

This reagent is used to differentiate between the structure of Aldehydes and methyl
Ketones.

10. Addition of Grignard reagent

Page 87 of 122
 Aldehydes generate Secondary Alcohol except ethanal while Ketones generate tertiary
alcohol.

R'MgX H2O RCHR' + Mg (OH)X

RCHO RCHR'
dry ether dil. HCl
OMgX OH

R'MgX H2O
HCHO R'CH2OMgX RCH2OH
dry ether dil.HCl

11. With Phosphorous penta chloride

Carbonyl compounds generate dichloride.

PCl5
RCHO RCHCl2
PCl5
RCOR' RCCl2R'

Distinguishing between Aldehydes and Ketones

Aldehydes can be differentiated from Ketones by various reagents that are oxidizing agent’ s i.e.

a) Ammoniacal Silver nitrate solution.

The reagent consists of silver nitrate in presence of excess ammonia solution.

Aldehydes react with ammoniacal silver nitrate form a silver mirror along side a clean
test tube on warming whereas no observable change for Ketones.

Ethanal reacts almost immediately.

RCHO + 2Ag(NH3)2OH RCOONH4 + 2Ag + H2O +3NH3

b) Fehling’ s test.

Aliphatic Aldehydes reduce copper (II) ions to reddish-brown copper (I) oxide on
heating.

RCHO + 2Cu2+ + NaOH + H2O RCOONa + Cu2O + 4H+

Ketones and aromatic Aldehydes give no observable change.

Reactions of Aromatic Aldehydes and Ketones involving substitution in Ring

Page 88 of 122
 Carbonyl group is deactivating group therefore the reaction involving the benzene ring
generatemeta-derivative product.
CHO
CHO
Conc. HNO3
Conc. H2SO4
NO2

CHAPTER NINE

CARBOXYLIC ACIDS

Introduction

Aliphatic monocarboxylic acids form a homologous series corresponding to the general

molecular formula, CnH2n+1COOH.

Carboxylic acids are organic compounds contain the carboxyl group that is made of carbonyl
group and hydroxyl group.

The number of the carboxyl group present in acid classifies acids as: Monocarboxylic acids
which are monobasic have one carboxyl while dicarboxylic acid are dibasic.

The simplest dicarboxylic acid are:

COOH
COOH COOH

COOH
COOH Butane-1,4-dioic acid
Ethanedioic acid COOH (Succinic acid)
Propane-1,3-dioic acid (Malonic acid)

Nomenclature

Page 89 of 122
The IUPAC names are afforded by taking the name of the appropriate alkane and replacing the
ending –“e” with the suffix “oic acid”. Positions of the substitution are denoted in the usual
way by numbering the longest unbranched chain containing the carboxyl group.

Sturcture Name
HCOOH methanoic acid

CH3CH2COOH Propanoic acid

CH3(CH2)2COOH Butanoic acid

(CH3)2CHCOOH 2-methylpropanoic acid

CH3(CH2)14COOH Hexadecanoic acid

C6H5CH2COOH 2-phenylethanoic acid
HOOCCOOH ethanedioic acid
HOOCCH2COOH Propane-1,3-dioic acid

Synthetic Preparations

1) Oxidation of Primary Alcohol or Aldehydes

Primary Alcohols or Aldehydes are oxidized by acidified potassium dichromate solution

or acidified chromium (VI) oxide to carboxylic acid.

CrO3 /H+ CrO3 /H+

RCHO RCOOH
RCH2OH
heat heat
Aldehyde Carboxylic acid
1oAlcohol

Orange solution turns green due to reduction of chromium (VI) ions to chromium (III)
ions.

2) Grignard synthesis

Mg CO2 H2O
RMgBr RCOOMgBr RCOOH + MgBrCl
RBr dil.HCl
dry ether dry ether
o o o
R may be 1 ,2 ,3 or Aromatic
Example

Mg CO2 H2O
CH3CH2Br CH3CH2MgBr CH3CH2COOMgBr CH3CH2COOH
dry ether dry ether dil.H+
In Preparation of Benzoic acid, solid carbondioxide or dry ice is used.

3) From Methyl Benzene

Page 90 of 122
 MnO4- /H+
CH3 COOH
heat

4) From Cyanide compounds.

KCN/EtOH H2O/H+
RX RCN RCOOH
heat Reflux

HBr KCN/EtOH
CH3CH CH2 CH3CH2CH2Br CH3CH2CH2CN
peroxide heat
H2O /H+ reflux

CH3CH2CH2COOH

The reaction is unsuitable for preparation of aromatic carboxylic acid.

5) Cannizzaro reaction

Aromatic Aldehydes and aliphatic ones containing no α-hydrogen atom undergo self
oxidation and reduction.

NaOH (aq) HCOONa + CH3OH

HCHO
dil.H+

HCOOH

6) Alkali Hydrolysis of Esters

The hydrolysis of Esters generates the corresponding alcohol and Acid.

The method is not commonly used since esters are obtained from carboxylic acid.

NaOH (aq)
RCOOR' RCOONa + R'OH

dil.H+

RCOOH

Physical Properties of Carboxylic acids

All simple aliphatic acids as far as C10 are liquids at room temperature while aromatic acids are
crystalline solids. Ethanoic acid has a sharp, pungent odour.

Page 91 of 122
Boiling points of the acids increase with increase molecular mass. The boiling points are higher
than expected because of the ability of the molecule to associate through hydrogen bonding
which requires extra energy to break.

The first four aliphatic acids are completely miscible with water due to the ability of the
functional group to form hydrogen bonds with water molecules.

Because of their greater hydrocarbon hence covalent character, the higher homologues
become progressively less soluble in water.

Benzoic acid is only slightly soluble in cold water but dissolves readily in hot.

N.B. The molecular mass determination of carboxylic acids using Colligative properties such as
freezing point in non-polar solvents gives the results that are twice than expected due
dimerisation of the molecule through hydrogen bonding in such solvents.

Acidic nature of carboxylic acids

Carboxylic acids are weak acids which partially dissociate in aqueous solutions. However, they
are stronger acids than alcohols and phenols.

The acidic strength of carboxylic acids depend on degree of ionisation and the acid dissociation
constant denoted Ka defined as

Ka = for a weak monobasic HX acid.

The Nature of the groups close to the carboxyl group has a great effect on the acid strength
therefore a phenomenon known as inductive effect.

Electron withdrawing groups’ e.g halogens makes carboxylic acid stronger thus oxygen-
hydrogen bond becomes weaken hence release of hydrogen ions in aqueous solution. i.e.

Acid CH3COOH CH2ClCOOH CHCl2COOH CCl3COOH

Ka 1.7x 10-5 1.3x10-3 5.0x10-2 2.3x10-1

1.29 0.65
PKa 4.76 2.86

Electron releasing groups’ e.g alkyl groups makes carboxylic acid weaker thus oxygen-hydrogen
bond strengthen hence less amount of hydrogen ions in aqueous solution.

Page 92 of 122
Reactions of carboxylic acids

The reactions of carboxylic acids involve the hydroxyl group which either undergoes the loss of
proton or replaced by another atom or group.

Some of the reactions include:

1) With Bases

The react to form salts and water

RCOOH + NaOH RCOONa + H2O

2) With electropositive metals.

The react to form salts and hydrogen

2 RCOOH + Mg (RCOO)2Mg + H2

3) With sodium carbonate or Sodium hydrogen carbonate

They react to liberate carbondioxide gas. They are stronger acids than carbonic acid.

2RCOOH + Na2CO3 2RCOONa + CO2 + H2O

RCOOH + NaHCO3 RCOONa + CO2 + H2O

4) With Primary Alcohols

Carboxylic acids react with primary alcohols in presence of concentrated sulphuric acid
as catalyst to form esters.

H+
RCOOH + R'OH RCOOR' + H2O
heat

(See Alcohols for mechanism of the reaction)

5) With Phosphorous Halides

They react to acid chlorides.

PCl5
RCOOH RCOCl + POCl3 + HCl
PCl3
RCOOH RCOCl + H3PO3

Page 93 of 122
6) With Thionyl chloride

They react also to form acid chlorides. This is the convenient method for preparation of
acid chlorides since the other two products are gaseous.

SOCl2
RCOOH RCOCl + SO2 + HCl
(white fumes)

7) With Iron (III) chloride solution

They react forming a reddish-brown precipitate or solution. Lower molecular mass acids
form a solution.

3RCOO- + Fe3+ (RCOO)3Fe

3C6H5COO-(aq) + Fe3+ (aq) (C6H5COO)3Fe (s)

8) Reduction reaction

Carboxylic acids are reduced to primary alcohols using lithium aluminium hydride.

LiAlH4
RCOOH RCH2OH
dry ether

9) Reaction of the Alkyl group

When chlorine gas is bubbled through hot carboxylic acid in presence of ultraviolet light,
one or all the hydrogen atoms adjacent are substituted.

Cl2 Cl2 Cl2

CH3COOH ClCH2COOH Cl2CHCOOH Cl3CCOOH
U.V.light U.V.light U.V.light

10) Decarboxylation reaction.

This reaction decreases the carbon length of the sodium salt of carboxylic acid to form
an alkane.

sodalime
RCOONa RH + Na2CO3
heat (Alkane)

Page 94 of 122
11) Amide formation.

SOCl2 NH3 LiAlH4 RCH2NH2

RCOCl RCONH2 dry ether
RCOOH
(Amide)

Br2 / Conc.NaOH (aq) heat

RNH2
Sample reaction scheme is shown below
SOCl2 CH3NH2 CH3CONHCH3
CH3COOH CH3COCl

NH3 Br2 / LiAlH4 dry ether

conc. NaOH (aq) heat
heat
H+ /H2O

CH3CONH2
CH3NHCH3 CH3CH2NHCH3
Br2 /
heat
conc. NaOH (aq)

CH3Br
CH3NH2

12) With Ammoniacal Silver nitrate solution

Methanoic acid is the only carboxylic acid that reacts with ammoniacal silver nitrate
solution on warming due to presence of Aldehydes group to form silver mirror along
side a clean test tube.

HCOOH + 2Ag+ CO2 + 2H+ +Ag

13) Dehydration reaction

Methanoic acid and Ethanedioic acid are the only carboxylic acid that can be dehydrated
using concentrated sulphuric acid.

conc. H2SO4
HCOOH CO + H2O
conc.H2SO4
(COOH)2 CO + CO2 + H2O

Question

Page 95 of 122
 1. How would one carry out the following conversions in the laboratory? Indicate the
necessary conditions of the reaction.

(a) CH3CHO to CH3COOCH3

(b) CH2 CH2 to CH3CH2COOH

(c) CH3COOH to CH3CH2NHCH3

(d) C6H5CH3 to C6H5COOCH3

2. Three isomeric acids A, B and C have molecular formula C8H6O4 and all contain a
benzene ring. In each case, one mole of the acid will react with 2moles of sodium
hydroxide. Suggest structures for the acids. When the three acids are separately heated,
A and B melt without decomposing, but C loses a molecule of water at about 250oC to
form D,C8H4O3.Suggest structures of C and D

3. Explain the following observations:

a) When dilute hydrochloric acid is added to aqueous solution of soap, a white

insoluble substance is formed.

b) Butane, Propan-1-ol, Propanal and Ethanoic acid have approximately the same
molecular mass yet their boiling points are 273, 370 and 391K respectively.

c) Methanoic acid reacts with ammoniacal silver nitrate solution while Ethanoic acid
does not.

d) Ethanedioic acid decolorizes potassium manganate (VII) solution on warming while

Ethanoic acid does not.

READ ON THE FOLLOWING ASPECTS

DERIVATIVES OF CARBOXYLIC ACIDS

 AMIDES

 ACID CHLORIDES

 ACID ANHYDRIDES AND ESTERS

Page 96 of 122
 CHAPTER TEN

AMINES

Introduction

Amines are alkyl or aryl derivatives of ammonia, and may be classified as Primary, secondary
and tertiary according to the number of alkyl or aryl groups attached to the nitrogen atom.

Aromatic amines are amines in which the nitrogen atom is attached directly to the aromatic
ring.

Compounds containing two amine groups are known as diamines.

Examples of amines are their classes include

NH2 N(CH3)2

CH3NH2 CH3NHCH3
methylamine, 1o dimethylamine, 2o

N,N-dimethylphenylamine, 3o
Phenylamine,1o
(CH3)3N
Trimethylamine,3o

Nomenclature

Both aliphatic and aromatic amines can be named by inserting the ending “amine” to the name
of alkane or other appropriate hydrocarbon.

Examples include:

CH3NH2 CH3CH2NH2 (CH3)2NH CH3CH2CH2NH2

Merthylamine Ethylamine Dimethylamine Propylamine

CH3CHNH2 CH3CH2NHCH3
N-Methylphenylamine
CH3
1-methylethylamine Ethylmethylamine
NHCH3

CH3CH2CH2NCH2CH3

CH3
N-ethyl-N-methylpropylamine

More complex tertiary amines with different alkyl groups are named as derivatives of the
longest chain and “N” is inserted before the named of each group.

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For aromatic amines, the names are derived from the simplest aromatic amine i.e.
Phenylamine.

Methylphenylamines are collectively termed as Toluidines.

Synthetic Preparation

1) From Alkyl halides

This method generates a mixture of amines. Therefore their separation fractional distillation is
used.

However better yield are obtained when Primary amine reacts with haloalkane compounds to
generate secondary or tertiary amine.

The method also is suitable for preparation of Aromatic amine since aromatic halides do not
react with ammonia under normal condition.

NH3
RCH2X RCH2NH2 + HCl

RCH2NH2 + RCH2X RCH2NHCH2R + HCl

RCH2NHCH2R + RCH2X (RCH2)3N + HCl

2) Reduction of Nitro compounds

Nitro compounds are reduced to Primary amines using Lithium Aluminium hydride or
hydrogen gas in presence of a catalyst.

LiAlH4
RCH2NO2 RCH2NH2
dry ether

CH3CH2NO2 LiAlH4
CH3CH2NH2
dry ether

For aromatic amines, tin and concentrated hydrochloric acid is used for reduction of
aromatic nitro compounds.

(i) Sn / Conc. HCl NH2

NO2
(ii) Conc. NaOH (aq), heat

3) Reduction of Nitriles

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 Nitriles are reduced to primary amines by lithium aluminium hydride or hydrogen in
presence of a catalyst.

LiAlH4
RCN RCH2NH2
dry ether

LiAlH4
CH3CH2Br KCN / EtOH CH3CH2CN CH3CH2NH2
heat dry ether

A further application is reduction of Oximes.

H2NOH LiAlH4
RCHO RCH NOH RCH2NH2
dry ether

4) Hofmann degradation of Amides.

This reaction gives a good yield of primary amine of a lower carbon chain.

Br2 / Conc. NaOH (aq)

RCONH2 RNH2 + 2NaBr + Na2CO3 +2H2O
heat

Br2 / Conc. NaOH (aq)

CH3CONH2 CH3NH2
heat methylamine
Ethanamide

5) Reduction of amides

Primary or Secondary or tertiary amides are reduced to their respective amines using
lithium aluminium hydride in dry ether.

LiAlH4
RCONH2 RCH2NH2
dry ether

Properties of Amines

Simple aliphatic amines are gases and possess a characteristic smell of ammonia. However most
of the higher homologues are liquids with rotten fish smell.

They are polar compounds and the molecules form intermolecular hydrogen bonds with each
other except tertiary amines.

For isomeric amines, the boiling points decrease in the order of 1o>2o>3o due to progressive
decrease in intermolecular hydrogen bond.

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The hydrogen bonds in alcohols are stronger than those in amines because oxygen is more
electronegative than nitrogen atom therefore the boiling points of alcohols are higher those of
amines of relatively the same molecular mass.

Lower molecular mass amines are soluble in water because the molecules form hydrogen bond
with water molecules and the resultant solution is basic .i.e. turns red litmus blue.

Basic Strength of Amines

The basic strength of amines depends on availability of lone pair of electrons on the nitrogen
atom for protonation. Primary amines are more basic than ammonia due to presence of alkyl
group which is electron releasing group therefore great salvation.

Secondary amines are more basic than Primary amines since they have two electron releasing
groups hence more solvation.

Tertiary amines are less basic than both Primary and Secondary amines but more basic
ammonia since they have three alkyl groups which are electron releasing groups’ hence greater
positive inductive effect or more electron releasing hence less solvation due to steric
hinderance.

Aromatic amines are weaker or less basic than aliphatic amines because of the presence of
benzene ring where the lone pair of electrons on the nitrogen atom gets delocalized.Thus lone
pair of electrons on the nitrogen atom becomes less available for protonation.

The Table gives the base dissociation and their boiling points of amines.

Amines M.p.t (oC) B.p.t(oC) Kb

CH3CH2NH2 -84 17 5.6X10-4
CH3CH2NHCH2CH3 -48 56 9.6X10-4
(CH3CH2)3N -115 90 5.7X10-4
C6H5N(CH3)2 3 194 11.5X10-5

Reaction of Amines

Majority of the reactions of amines indicate aminesaselectron rich species (Nucleophiles).

Therefore some of the reactions of amines include:

1) Salt formation

As bases, amines react with acids to form salts.

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 + -
RNH2 + HX RNH3X

HCl + -
CH3CH2NH2 CH3CH2NH3Cl

Generally the salts are soluble in water but insoluble in organic solvents. Therefore
amines are soluble in dilute mineral acids.

2) Amide formation

Both aliphatic and aromatic primary or secondary amines readily acylated using acyl
halides or acid anhydrides

RCOCl + R'NH2 RCONHR' + HCl

CH3COCl + CH3NH2 CH3CONHCH3 + HCl

RNH2 + (R'CO)2O RNHCOR' + R'COOH

C6H5NH2 + (CH3CO)2O C6H5NHCOCH3 + CH3COOH

Qn: Write the mechanism of the above reaction

3) Alkylation of amines

Primary and secondary halides react with amines to form alkylated amine.

RCH2X + R'CH2NH2 RCH2NHCH2R' + HX

(RCH2)2NH + R'CH2X (RCH2)2NCH2R' + HX

Qn: Write the mechanism of the above general reactions.

4) With Nitrous acid

Nitrous acid is unstable at room temperature therefore usually prepared in the reaction
mixture using sodium nitrite and concentrated hydrochloric acid at low temperatures
usually below 10oC.

The reaction mixture is used to differentiate between the classes of amines.

a) With Primary Aliphatic amines

They react to unstable alkyl Diazonium salt that decomposes to a colourless solution and
bubbles of colourless gas.

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 HNO2
RNH2 ROH + N2 + mixture of ethers, alkene,haloalkane
o
< 10 C

b) With Secondary amines

Both aliphatic and aromatic secondary amines react forming yellow oily liquids.

HNO2
RNHR' R N N O + H2O
o
< 10 C
R'
N- nitrosoamines

c) With Tertiary amines

They with nitrous acid forming a colourless solution without evolution of bubbles of a
colourless gas

HNO2 + -
R 3N R3NHNO2
< 10oC

d) With Primary Aromatic amines

They react forming benzene Diazonium salt which is a stable colourless solution below 10 oC.

The reaction between primary aromatic amine with nitrous below 10 oC is known as
diazotization.

NaNO2 / conc.HCl + -
NH2 N NCl + H2O
< 10oC

Benzene diazonium salt

Above 10oC, there is effervescence of a colourless gas and colourless liquid of phenol.

NaNO2 / conc.HCl
NH2 OH + N2
> 10oC

Reactions of Benzene Diazonium salt

Benzene Diazonium salt are prepared by action of nitrous acid on Phenylamine below 10oC.

They undergo two types of reactions i.e.

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1) Nucleophilic substitution reaction

a) With water.

+ H2O
N NCl OH + N2
warm

b) Halogen substitution

CuCl /conc. HCl

Cl
Warm

+
N NCl
KI
I
Warm

CuBr /conc.HBr
Br
Warm

c) Cyanide substitution

+ CuCN / KCN
N NCl
CN
Warm

2) Coupling reactions

These reactions are usually used to generate azo dyes.

a) With Phenol

In alkaline medium benzene Diazonium salt react with phenol form a yellow azo dye.
H
+
N N O- N N O

H+ shift

N N OH

4-hydroxphenylazobenzene
(Yellow solid)

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b) With Napth-2-ol

Benzene Diazonium salt forms a red azo dye in presence of alkaline medium also.

OH

OH
+ NaOH (aq) N N
N N+

1-phenyl-2-azo-napthol
( red solid)

c) With amines

+
N N + N(CH3)2 N N N(CH3)2

4-dimethylaminoazobenzene
(Yellow solid)

Qn: Write the mechanism of this reaction

Reaction of Aromatic amines (Substitution in the Benzene ring)

The amino group directs the incoming group to position 2 and 4 and activates the benzene ring
towards Electrophilic substitution reactions.

Phenylamine reacts with Bromine forming a white precipitate of 2,4,6-tribromophenylamine.

NH2
NH2
Br Br

+ 3Br2
+ 3HBr

Br

Page 104 of 122

CHAPTER ELEVEN

SOAP AND DETERGENTS

SOAP

Sodium salt of long carboxylic acid is known as soap. Soap is usually obtained from Fats or Oils.

Fats and Oils are complex mixtures of glycerol with a long chain carboxylic acid. Fats are solids
at room temperature while Oils are liquids.

Fats tend to contain greater proportion of unsaturated acids while Oils tend to contain greater
proportion of saturated acids.

The sources of oils are cotton seed, simsim, groundnut, sunflower seed, soya beans and
coconut etc while fats are obtained from animals such as Pigs, Sheep or Cows.

Preparation of Soap

Soap is prepared by a reaction known as saponification.

Roast the dry seeds; crush/grind to make paste. Boil with water until oil floats on top and
decant off the oil. Mix the oil with excess sodium hydroxide solution and boil while constant
stirring for a long time.

CH2OCOR CH2OH
NaOH (aq) 3RCOONa +
CHOCOR CHOH
heat CH2OH
CH2OCOR Sodium salt
Fat or Oil of carboxylic acid Glycerol

Add concentrated sodium chloride solution (Brine) to precipitate out the soap.

Cleansing Action of Soap

Soap lowers the surface tension between water and oil or insoluble material. They do so
because they contain a polar group (-COO-) and a non-polar alkyl chain (R-). The molecule of
water congregates near the polar end while the molecules of oil congregate around the alkyl
group. The non-polar oil particles are emulsified into suspension and removed.

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N.B. Hard water affects the cleansing action of soap. Hard water contains calcium or
magnesium ions. These ions react with soap to form a precipitate known as Scum.

2RCOONa (aq) + Ca2+ (aq) (RCOO)2Ca (s) + Na+ (aq)

Lather cannot be formed when the entire calcium or magnesium ions are completely removed
as scum. This wastes soap in hard water.

DETERGENTS

These are substances which improve the cleansing properties of water since they are sodium
salts of long chain alkyl sulphonate or alkyl sulphate

Features of Detergents

Detergents have along chain hydrocarbon end which is oil or Fat soluble and hydrophilic part
which is the sulphonate group. Thus detergents are sodium salts of sulphonic acids.

Since Detergents are alkyl benzene sulphonate examples include:

R SO3-Na+ CH3(CH2)10C SO3-Na+

Common detergents include Nomi, Omo, surf, teepol etc.

Properties of detergents

1. They are highly soluble in water

2. Detergents are emulsifying agents.

Preparation of Alkyl Benzene sulphonate

Soap less detergent is prepared as follows:

Benzene is alkylated in presence of a halogen carrier. The alkylated benzene is then

sulphonated with concentrated sulphuric acid and the sulphonic acid formed is reacted with
sodium hydroxide solution to form the detergent. i.e.

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 CH2(CH2)10CH3

AlCl3
CH3(CH2)9CH CH2 +

conc.H2SO4

CH2(CH2)10CH3 CH2(CH2)10CH3

NaOH (aq)
heat
SO3H
SO3-Na+

The table below shows the types of detergents and their uses.

Types Nature use

Anionic detergent
Cationic detergent
Non-ionic detergents
These have negative heads
e.g CH3(CH2)11CH2OSO3-Na+
These have positive heads
e.g C15H31N(CH3)3Br
These are neutral in water
i.e. these carry no charge
Used for manufacture of
toothpaste and shampoo
Used for hair conditioners
Used for making liquid
detergents

Action of Detergents on Fabrics

The action of detergents on fabrics is the same as that of soap.

Detergent Additives

1) Sodium Sulphate: This is used to increase the bulk of the detergent.

2) Detergent builders (Inorganic phosphate): These are used as water softeners because
they form soluble complexes with calcium or magnesium ions in hard water.

3) Peroxyborates: These are used as bleaching agents.

Advantages of Soap over detergents

a) Soap is biologically degradable

b) Soap can be used for both bathing and washing

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Disadvantage of Soap over detergents

They form undesirable scum with hard water which leads to wastage of soap

Advantages of detergents over soap

a) They are used in any of water.

b) Detergents have a brighter cleansing effect

Disadvantages of detergents over soap

a) Detergents are non biodegradable

b) Detergents contain fertilizer materials such as phosphates which nourish the growth of
algae hence reducing oxygen supply in water.

Question:

a) Some oils are used in the manufacture of soap.

i. Name the reaction leading to the formation of soap

ii. Outline how soap is manufactured from oil.

iii. Write an equation of reaction between hard water and soap

iv. Explain briefly why soap is not commonly used in washing aluminium utensils

v. A sample of soap was prepared from 9.5g of oil containing an ester of hexadecanoic acid
(C15H31COOH). Calculate the mass of soap formed.

b) Synthetic detergents are gradually replacing soap as cleansing agents.

i. Write equations to show how a soap less detergent can be prepared from
CH3(CH2)5CH CH2

ii. What problem does detergent cause to the environment

iii. State one structural difference between soap and detergent

iv. Describe the cleansing action of Omo as a detergent

v. 0.6cm3 of Jik was dissolved in water and solution made in 250cm3 volumetric flask.
25cm3 of this solution was acidified and 10cm3 of 0.2M potassium iodide solution added.

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 The iodine liberated required 5.0cm3 of 0.2M Sodium thiosulphate solution for complete
reaction. Calculate the mass of Chlorine in 1dm3 of Jik.

POLYMERISATION

This is the building of large molecules (polymer) by linking together very many small molecules
(monomers) with or without loss of small molecules such as water, ammonia etc.

Polymers are long chain molecules with recurring structural units formed by polymerization
process.

When the recurring units are different, a co-polymer is formed.

Factors that determine the properties of Polymers

 Chain length: Strength and melting points of polymers increase with increase chain
length

 Branching: Increased branching reduces the molecular strength and lowers the melting
point

 Cross linkage: Polymers with a cross link between the chains form a rigid network which
increases the strength.

 Intermolecular forces: Stronger intermolecular forces between the chains result into
higher melting points.

Types of Polymers

1. Natural Polymers

These are polymers whose formation is not controlled by man. These include Cellulose material
(Cotton, paper), Protein material (wool, silk), Natural rubber and Rayon.

2. Synthetic Polymers

These are polymers that are man made. These include Plastics and fibers, addition polymers
(polyethene, polypropene, and polyvinylchloride), Condensation polymers (Polyesters, nylon 6,
6)

Natural Rubber

Rubber is obtained naturally from rubber trees as milky liquid called latex.

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Natural rubber is a polymer derived from 2-methylbut-1, 3-diene I,e

H
CH2C CHCH
HC CCH CH2
H
CH3 CH3
n
2-methylbut-1,3-diene Natural rubber (polymer)
(monomer)

Natural rubber is very soft and of little use. It is made hard and tough by heating it with sulphur
by a process known as Vulcanisation.

Vulcanisation

This is the process of improving on the qualities of rubber by heating it with sulphur.

The sulphur atoms add to some double bonds of two neighbouring rubber molecules to form
vulcanized rubber.

The hardness of vulcanized rubber is directly proportional to the amount of sulphur added.

The following are the effects of heating natural rubber with sulphur:

 It improves on temperature working range

 It improves on toughness

 It improves on elasticity

 It improves on Bulkiness

Vulcanized rubber therefore is used for making car tyres, shoe sole, gloves and insulating
electric cables.

Synthetic Polymer

Addition Polymers

Addition Polymerization

This is the building up of a large molecule from a number of unsaturated monomers to form a
single product.

Addition polymers include:

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Polyethene: These exsit in two forms i.e. High density and lower density polymer.

Low density polymer: This is formed in presence of a catalyst i.e.

200oC / O2
CH2 CH2 * CH2CH2 *
1200atm

Low density polyethene is used for making plastic bags, packing materials, electric cables,
insulators.

High density polyethene: This is formed when ethene undergoes polymerization at 60oC and 1
atmosphere. i.e.

60oC
CH2 CH2 * CH2CH2 *
1atm

High density polyethene is used for manufacture of water tanks, plastic pipes, plastic bottles,
crates, buckets and kitchen ware.

Polyethenedon’ trot, insoluble in most common solvents and less dense than water.

Polyvinylchloride (PVC)

The monomer is chloroethene. Chloroethene undergoes polymerization at high pressure and

temperature in presence of peroxide i.e.

high Temp /Pressure

ClCH CH2 * CH2CH *
peroxide
n
Cl

The properties of PVC are water proof, non-degradable, not attacked and easily destroyed on
heating.

PVC is used for making plastic coats, umbrellas, electronic equipments, suitcases and insulating
electric cables.

Polypropene

This is formed from propene at 100oC and 100atmosphere in presence of peroxide.

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 100oC / 100atm
nCH3CH CH2 CHCH2 *
peroxide
CH3
n

Polypropene is used for making beer bottle crates, drinking straws, ropes and surfaces of all
weather football and hockey pitches.

Polystyrene / Polyphenylethene

The monomer is phenylethene. Polystyrene is used for making combs, packing materials,
ceilings and toys.

Perspex

CH3

CCOOCH3
This is an addition polymer whose monomer is H2C .

Perspex is used for making lenses, laboratory glass ware, windows of cars and airplanes,
corrugated roof lights and in packaging.

Condensation Polymers

Condensation polymerization occurs when molecules that are bifunctional or polyfunctional

react together to form a polymer and another product with small molecules.

Nylon 6,6

The monomers are diaminohexane and hexanedioic acid. It is called Nylon 6, 6 because each of
the monomers has got six carbon atoms.

O O

NH2(CH2)6NH2 + HOOC(CH2)4COOH NH(CH2)6NHC(CH2)4C * + H2O

diaminohexane Hexanedioic acid

n
Nylon 6,6

Nylon 6,6 has the following properties:

 It is water repellent hence dries easily

 It has got a hard warring tendency

 Insoluble in most solvents

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  Fuses at temperatures above 200oC

Nylon 6,6 is used for making of stockings, gloves, clothes, carpets and fishing nets.

N.B. Nylon 6,10 has monomers 1,6-diaminohexane and decanedicyldichloride and it is used for
making surgical gloves, curtains , fishing nets and carpets.

Nylon polymers are also known as polyamides since they contain the peptide bond with in
the molecule.

Polyester / Terylene

Made by condensing Ethane-1,2-diol and Benzene-1,4-dicarboxylic acid with loss of water

molecules. i.e.

O O

HOCH2CH2OH + HOOC COOH * OCH2CH2OC C *+ H2O

n

It is used for making clothes (textiles), ropes, safety belts and tents.

Differences between Addition polymerization and Condensation polymerization

Addition polymerization Condensation polymerization

1 Addition polymers are linear Condensation polymers are non-linear

2 The monomers used are similar Monomers used are different

3 Addition polymerization can be reversed Condensation polymerization is irreversible

Advantages of Synthetic polymers over natural polymers

 Easier to manufacture

 Relatively stronger than the corresponding natural polymer

Disadvantages of Synthetic polymers over Natural polymers

 Non-biodegradable

 Its manufacture involves release of toxic fumes which cause a health hazards to Human.

Page 113 of 122

Plastics

A plastic is a substance which when heated becomes soft and can be moulded into different
shapes.

Properties of Plastics

 Become soft on heating

 Non-biodegradable

 Not attacked by acids or alkali

The properties of plastics can be modified by addition of:

 Plasticizers: these are substances which soften and make plastics easily moulded.

 Dyes and pigments: used to colour plastics

 Fillers: are used to increase the bulk of Plastics.

Types of plastics

1) Thermosofthening plastics (Thermoplastics)

These are plastics which when heated soften and can be remoulded into different shapes. This
is because the binding forces between the polymer chains are weak and also have fewer cross-
linkages between the polymer chains (or linear pattern arrangement).

Thermoplastics include Polypropene, polyethene, polystyrene, polyvinylchloride etc.

2) Thermosetting plastics (Thermosets)

These are plastics which when heated donot soften but harden and can not be remoulded in to
different shapes. This is because they are held together by much cross-linkage between the
polymer chains.

Thermosets include Bakelite used for making electric plugs, sockets and switches.

Advantages of Plastics over metals

 Plastics are resistant to attacks by acids, alkalis and atmospheric oxygen (corrosion).

 Easier to be recycled.

 Lighter than metals

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Disadvantages of Plastics over metals

 Plastics items easily burn

 Pollutants since they are non-biodegradable

 You are provided with organic substance Z whose nature is required to be determined.
Record your observation(s) and deduction(s) in the table below

Sample OrganicPractical’ s

Sample one

You are provided with organic substance Z whose nature is required to be determined. Record
your observation(s) and deduction(s) in the table below

TEST OBSERVATION(S) DEDUCTION(S)

(a) Burn a small amount of Z Burns with non-sooty flame Aliphatic compound present
on crucible lid.

b) To 1cm3 of Z, add 2cm3 of Soluble in water. Solution is Alcohols, carbonyl compounds

water and shake the mixture.
Test with litmus.
c) To 1cm3 of Z, add five drops
of Brady’ s reagent.
(d) To 2cm3 of Z, add acidified
Potassium dichromate and
warm.
(e) To 2cm3 of Z, add Lucas
reagent.
(e) To 2cm3 of Z, add conc.
Sulphuric acid, heat and pass
the vapour through acidified
Potassium permanganate
solution.
neutral to litmus
No observable change
Or
No yellow precipitate formed
Orange solution turns green
Cloudiness formed after a
short time.
Colourless gas turns acidified
Purple solution turns
colourless
present
Carbonyl compound absent
Primary, secondary alcohol
probably present
Secondary alcohol present
Dehydration of alcohol
leading to formation of an
alkene.

Page 115 of 122

(f) To 1cm3 of Z, add Iodine
solution followed by sodium
hydroxide solution drop wise
until the Iodine is discharge
and warm.
Yellow precipitate Secondary alcohol contains a
methyl radical adjacent to the
carbon atom carrying the
functional group

Comment on the nature of Z

Z is an aliphatic secondary alcohol with structure

RCHCH3

OH

Sample Practical Two

You are provided with organic substance K. You are required to identify the nature of K. Carry
out the following tests on K and record your observations and deductions in the table below.

TEST OBSERVATION(S) DEDUCTION(S)

(a) Burn a spatula end -ful of K Burns with non-sooty flame Aliphatic compound present
on a porcelain dish.

(b) Shake 3cm3 of K with 2cm3
of water and allow to it stand.
Test with litmus.
(c )To 2cm3 of K in test tube,
add Brady’ s reagent.
Soluble in water. Solution is Alcohol , Carbonyl compounds
neutral to litmus probably present
Yellow precipitate formed Carbonyl compound present

(d)To 2cm3 of K, add saturated White precipitate formed Carbonyl compound present
sodium hydrogen sulphite
solution.

(e) To 1cm3 of K in the test No observable change Aldehydes absent

tube, add acidified potassium Or
dichromate and warm. Ketones present

(f) To 3cm3 of silver nitrate No silver mirror formed Aldehydes absent

solution, add 2cm3 of sodium

Page 116 of 122

hydroxide then ammonia drop Or Or
wise until the precipitate No observable change
3
dissolves followed by 3cm of Ketones present
K. Then warm.

(g) To 2cm3 of K, add iodine
followed by sodium hydroxide
until the colour is discharged.
Warm the mixture and cool
under water.
Yellow precipitate formed Methyl radical attached to the
carbon atom carrying the
functional group.

(h) Comment on the nature of K

K is aliphatic carbonyl compound with a structure of

O
R C CH3

Sample Practical Three

You are provided with an organic substance J whose nature is required to be determined. Carry
out the following test on J.

TEST OBSERVATION(S) DEDUCTION(S)

a) Burn a small amount of J in Burns with yellow sooty flame Aromatic compound present
a spatula.

b) To a half spatula end ful of Slightly soluble in water. Phenol or Carboxylic acid
J, add 1cm3 of water and with Solution turns methyl orange present
test with methyl orange pink / red
indicator.
c) To a half spatula end ful of No violet colouration formed Phenol absent
J, add 2-3 drops of iron (III)
chloride solution.

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d) Boil a spatula end ful of J
with sodium hydroxide
solution for three minutes.
e) Add sodium carbonate
solution to about a spatula
end ful of J.
f) Add a spatula endful of J
in about 2cm3 of water
followed by acidified
potassium manganate(VII)
solution
f) Add 1cm3 of ethanol to a
spatula end ful of J followed
by concentrated sulphuric
acid. Boil the mixture and
pour into a beaker of water.
g) Add 3cm3 of water to a
spatula end-ful of J in a test
tube. Then add soda lime and
Heat strongly.
(h) Comment on the nature of J
J is an aromatic unsaturated compound with a carboxyl group attached.
Sample Practical Four
You are provided with an organic compound Q. You are required to determine the nature of Q.
Carry out the following tests on Q and record your observations and deductions in the table
below.
Tests
a) Burn a small amount of Q
on crucible lid
Dissolves to form a colourless
solution
Slight effervescence
Or
Bubbles of colourless gas
Purple solution turns
colourless
Sweet fruity smell formed
Colourless gas formed
Observations
Burns with a yellow sooty
flame
Page 118 of 122
Acidic compound present
Therefore carboxylic acid
present.
Carboxylic acid present
Compound is Unsaturated
Esterification occurred
Therefore Carboxylic acid
present.
Decarboxylation occurred
Therefore Carboxylic acid
present.
Deductions
Aromatic compound present
b)Add a spatula end-ful of Q
to about 3cm3 of dilute
sodium hydroxide solution
and shake
c) To a spatula end ful of Q in
a test tube add 4cm3 of water.
Shake vigorously and warm.
Test the solution with litmus
paper and divide the resultant
solution into three portion
(i) To the first portion, add
three drops of 2,3-
dinitrophenylhydrazine
(ii) To the second portion, add
3 drops of iron (III) chloride
solution
(iii) To the third portion, add
endful of solid sodium
hydrogen carbonate
d) To 3cm3 of methanol, add a
spatula end-ful of Q and
shake. Add 3-4 drops of
concentrated sulphuric acid
and warm the mixture
Soluble to form a colourless
solution
Slightly soluble in cold water
and soluble on warming.
Turns blue litmus red
No observable change
Or
No yellow precipitate formed
Violet colouration formed
Effervescence occurred
Or
Bubbles of colourless gas
Sweet fruity smell
Acidic compound present.
Therefore Phenol ,carboxylic
acid probably present
Phenol, Carboxylic acid
probably present
Carbonyl compound absent
Phenol absent
Carboxylic acid present
Esterification occurred
Therefore carboxylic acid
confirmed.

(e) Comment on the nature of Q

Aromatic compound with a hydroxyl and carboxyl groups attached to benzene ring.

Sample Practical Five

You are provided with organic substance J whose nature is required to be determined.

Carry out the following tests on J and identify the functional groups in J.

TEST OBSERVATION(S) DEDUCTION(S)

a) Burn a small amount of J in Burns with yellow sooty flame Aromatic compound present
a crucible lid.

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b) To 2cm3 of J, add 2cm3 of Slightly soluble in water. Alcohol or Carbonyl compound
water and warm the mixture Solution is neutral to litmus. probably present
and test with litmus paper.
Divide the warm solution into
four parts.
(i) To the first part, add 2-3 No observable change Carboxylic acid absent
drops of sodium carbonate
solution.
(ii) To the second part, add 2-3 No observable change Phenol absent
drops of iron (III) chloride Or
solution. No violet colouration formed
(iii)To the third part add 2,4- Yellow precipitate formed Carbonyl compound present
dinitrophenylhydrazine solid
followed by 2cm3 of
ofconcentrated sulphuric acid.
(iv) To the fourth part, add 2- Orange solution turns green Aldehydes present
3drops of acidified potassium Or
dichromate solution and Ketones absent
warm.
c) To 2cm3of J, add silver Silver mirror formed Aldehydes present
nitrate solution followed by
sodium hydroxide solution
then ammonia solution until
the solid dissolves. Warm the
mixture.
d) To 3cm3 of J, add iodine No observable change Methyl Aldehyde absent
solution followed by sodium
hydroxide solution and warm Or
the mixture No yellow precipitate formed
e) To 3cm3 of J, add Fehling Brown precipitate formed Aldehyde present
solution and heat the mixture

f) To 3cm3 of J, add acidified Purple solution turns Compound is unsaturated

potassium manganate (VII) colourless
solution.

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e) Comment on the nature of J

J is an unsaturated aromatic compound with a carbonyl group attached.

Sample Practical Six

You are provided with an organic substance Q. Carry out the following tests on Q to identify its
nature.

Record your observations and deductions in the table below.

Tests Observations Deductions

(a) Burn a small amount of Q Burns with a yellow sooty Aromatic compound present
on a spatula end flame
(b) Shake 3 drops of Q with Slightly soluble in water. Basic Compound present
about 3cm3 of water and test Solution turns red litmus to Therefore Amines present
with litmus blue
(c) Place 2cm3 of dilute White fumes are formed. Amines present
hydrochloric acid in a test Soluble in acid
tube followed by 3 drops of Q
(d) To 3drops of Q add Red precipitate formed Azo dye formed
concentrate hydrochloric acid Primary aromatic amine
until the mixture is just acidic present
the add 1cm3 of sodium
nitrite solution followed by 2-
napthol in sodium hydroxide
solution
(e) To 3drops of Q in a test White precipitate Primary Aromatic amine
tube add concentrate
hydrochloric acid until it
dissolves. Then add bromine
water drop by drop until in
excess.

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(f) To three drops of Q in a Purple solution turns Unsaturated compound
test tube,add acidified colourless present.
potassium manganate(VII)
solution.

Comment on the nature of Q

Q is unsaturated primary aromatic amine.

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